Platinum-free ruthenium-cobalt catalyst formulations for hydrogen generation

ABSTRACT

A method and catalysts and fuel processing apparatus for producing a hydrogen-rich gas, such as a hydrogen-rich syngas are disclosed. According to the method, a CO-containing gas, such as a syngas, contacts a platinum-free ruthenium-cobalt water gas shift (“WGS”) catalyst, in the presence of water and preferably at a temperature of less than about 450° C., to produce a hydrogen-rich gas, such as a hydrogen-rich syngas. Also disclosed is a platinum-free ruthenium-cobalt water gas shift catalyst formulated from:
         a) Ru, its oxides or mixtures thereof,   b) Co, Mo, their oxides or mixtures thereof, and   c) at least one of Li, Na, K, Rb, Cs, Ti, Zr, Cr, Fe, La, Ce, Eu, their oxides and mixtures thereof. The WGS catalyst may be supported on a carrier, such as any one member or a combination of alumina, zirconia, titania, ceria, magnesia, lanthania, niobia, zeolite, perovskite, silica clay, yttria and iron oxide. Fuel processors containing such water gas shift catalysts are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a Rule 1.53(b) Divisional Patent Applicationof U.S. patent application Ser. No. 10/739,988, filed Dec. 18, 2003,which is U.S. Pat. No. 7,160,534, issued Jan 9, 2007, before whichclaims benefit from earlier filed U.S. Provisional Application No.60/434,632, filed Dec. 20, 2002, abandoned, which are incorporatedherein in their entireties by reference for all purposes. The presentapplication also incorporates by reference the PCT International PatentApplication No. US2003/0040215 entitled “Platinum-Free Ruthenium-CobaltCatalyst Formulations for Hydrogen Generation” naming as inventorsHagemeyer et al. filed on Dec. 18, 2003.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to methods and catalysts for generating ahydrogen-rich gas from gas mixtures containing carbon monoxide andwater, such as water-containing syngas mixtures. More particularly, theinvention includes methods using platinum-free catalysts which containruthenium and cobalt, and ruthenium, cobalt and molybdenum. Thecatalysts may be supported on a variety of catalyst support materials.The ruthenium-cobalt catalysts of the invention exhibit both highactivity and selectivity to hydrogen generation and carbon monoxideoxidation.

2. Discussion of the Related Art

Numerous chemical and energy-producing processes require a hydrogen-richcomposition (e.g. feed stream.) A hydrogen-rich feed stream is typicallycombined with other reactants to carry out various processes. Nitrogenfixation processes, for example, produce ammonia by reacting feedstreams containing hydrogen and nitrogen under high pressures andtemperatures in the presence of a catalyst. Fuel cells such as polymerelectrode membrane (“PEM”) fuel cells, produce energy from ahydrogen-rich feed stream. PEM fuel cells typically operate with afeedstream gas inlet temperature of less than 450° C. Carbon monoxide isexcluded from the feed stream to the extent possible to preventpoisoning of the electrode catalyst, which is typically aplatinum-containing catalyst. See U.S. Pat. No. 6,299,995.

One route for producing a hydrogen-rich gas is hydrocarbon steamreforming. In a hydrocarbon steam reforming process steam is reactedwith a hydrocarbon fuel, such as methane, iso-octane, toluene, etc., toproduce hydrogen gas and carbon dioxide. The reaction, shown below withmethane (CH₄), is strongly endothermic:CH₄+2H₂O→4H₂+CO₂In the petrochemical industry, hydrocarbon steam reforming of naturalgas is typically performed at temperatures in excess of 900° C. Even forcatalyst assisted hydrocarbon steam reforming the temperaturerequirement is often still above 700° C. See, for example, U.S. Pat. No.6,303,098. Steam reforming of hydrocarbons such as methane, usingnickel- and gold-containing catalysts and temperatures greater than 450°C., is described in U.S. Pat. No. 5,997,835. The catalyzed process formsa hydrogen-rich gas, with depressed carbon formation.

One example of effective hydrocarbon steam reforming catalysts is theSinfelt compositions which are composed of Pt, a Group 11 metal, and aGroup 8 to 10 metal. Group 11 metals include Cu, Ag and Au while Group 8to 10 metals include the other noble metals. These catalyst formulationsare well known in the promotion of hydrogenation, hydrogenolysis,hydrocracking, dealkylation of aromatics, and naphtha reformingprocesses. See, for example, U.S. Pat. Nos. 3,567,625 and 3,953,368. Theapplication of catalysts based on the Sinfelt model to the water gasshift (“WGS”) reaction, in particular at conditions suitable for lowertemperature WGS applications such as PEM fuel cells, has not beenpreviously reported.

Purified hydrogen-containing feed streams have also been produced byfiltering the gas mixture produced by hydrocarbon steam reformationthrough hydrogen-permeable and hydrogen-selective membranes. See, forexample, U.S. Pat. No. 6,221,117. Such approaches suffer from drawbacksdue to the complexity of the system and slow flow rates through themembranes.

Another method of producing a hydrogen-rich gas such as a feed streamstarts with a gas mixture containing hydrogen and carbon monoxide withthe absence of any substantial amount of water. The carbon monoxide canbe removed by absorption and/or by its oxidation to carbon dioxide. Sucha process utilizing a ruthenium based catalyst to remove and oxidize thecarbon monoxide is disclosed in U.S. Pat. No. 6,190,430.

The WGS reaction provides another mechanism for producing ahydrogen-rich gas but from water (steam) and carbon monoxide. Anequilibrium process, the water gas shift reaction, shown below, convertswater and carbon monoxide to hydrogen and carbon dioxide, and viceversa.H₂O+CO

H₂+CO₂Various catalysts have been developed to catalyze the WGS reaction.These catalysts are typically intended for use at temperatures greaterthan 450° C. and/or pressures above 1 bar. For instance, U.S. Pat. No.5,030,440 relates to a palladium and platinum-containing catalystformulation for catalyzing the shift reaction at 550 to 650° C. See alsoU.S. Pat. No. 5,830,425 for an iron/copper based catalyst formulation.

Catalytic conversion of water and carbon monoxide under water gas shiftreaction conditions has historically been used to produce hydrogen-richand carbon monoxide-poor gas mixtures. Existing WGS catalysts, however,do not exhibit sufficient activity at a given temperature to reach oreven closely approach thermodynamic equilibrium concentrations ofhydrogen and carbon monoxide such that the product gas may subsequentlybe used as a hydrogen feed stream. Specifically, existing catalystformulations are not sufficiently active at low temperatures, i.e.temperatures below about 450° C. See U.S. Pat. No. 5,030,440.

Platinum (Pt) is a well-known catalyst for both hydrocarbon steamreforming and water gas shift reactions. Under the typical hydrocarbonsteam reforming conditions of high temperature (above 850° C.) and highpressure (greater than 10 bar), the WGS reaction may occurpost-reforming over the hydrocarbon steam reforming catalyst due to thehigh temperature and generally unselective catalyst compositions. See,for instance, U.S. Pat. Nos. 6,254,807; 5,368,835; 5,134,109 and5,030,440 for a variety of catalyst compositions and reaction conditionsunder which the water gas shift reaction may occur post-reforming. Adrawback to the use of Pt in catalyst compositions is its expense.

Metals such as cobalt (Co), ruthenium (Ru), palladium (Pd), rhodium (Rh)and nickel (Ni) have also been used as WGS catalysts but are normallytoo active for the selective WGS reaction and cause methanation of CO toCH₄ under typical reaction conditions. In other words, the hydrogenproduced by the water gas shift reaction combines with CO in thepresence of WGS catalysts to yield methane. This tendency towardmethanation has typically limited the utility of metals such as Co, Ru,Pd, Rh and Ni as water gas shift catalysts.

A need exists, therefore, for a method of producing a hydrogen-richsyngas using relatively inexpensive platinum-free catalysts which arehighly active and highly selective for both hydrogen generation andcarbon monoxide oxidation at moderate temperatures (i.e. below about450° C.) to provide a hydrogen-rich gas, such as a hydrogen-rich syngas,from a gas mixture containing, at least CO, and preferably hydrogen.

SUMMARY OF THE INVENTION

The invention meets the need for highly active and selectiveplatinum-free ruthenium-cobalt catalysts for the generation of hydrogenand the oxidation of carbon monoxide and to thereby provide ahydrogen-rich gas, such as a hydrogen-rich syngas, from a gas mixture ofat least carbon monoxide and water. Accordingly, the invention providesmethods and catalysts for producing a hydrogen-rich gas.

The invention is, in a first general embodiment, a method for producinga hydrogen-rich gas (e.g., syngas) by contacting a CO-containing gas,such as a syngas mixture, with a platinum-free water gas shift catalystin the presence of water at a temperature of not more than 450° C. Inthe first general embodiment, the water gas shift catalyst, with anessential absence of Pt, comprises (a) Ru, its oxides or mixturesthereof; (b) Co, Mo, their oxides or mixtures thereof; and (c) at leastone of Li, Na, K, Rb, Cs, Ti, Zr, Cr, Fe, La, Ce, Eu, their oxides andmixtures thereof. The catalyst may be supported on a carrier, forexample, at least one member selected from the group consisting ofalumina, zirconia, titania, ceria, magnesia, lanthania, niobia, zeolite,perovskite, silica clay, yttria, iron oxide and mixtures thereof. Themethod of the invention may be conducted at a temperature ranging fromabout 150° C. to about 450° C.

In a second general embodiment, the invention relates to the water gasshift catalysts themselves—both supported and unsupported catalysts. Ina more particularized first embodiment, the inventive water gas shiftcatalyst, with an essential absence of Pt, comprises (a) Ru, its oxidesor mixtures thereof; (b) Co, Mo, their oxides or mixtures thereof; and(c) at least one of Li, Na, K, Rb, Cs, Ti, Zr, Cr, Fe, La, Ce, Eu, theiroxides and mixtures thereof. The catalyst may be supported on a carriercomprising at least one member selected from the group consisting ofalumina, zirconia, titania, ceria, magnesia, lanthania, niobia, zeolite,perovskite, silica clay, yttria and iron oxide.

In a third general embodiment, the invention is directed to theaforementioned water gas shift catalysts of the second generalembodiment in an apparatus for generating a hydrogen gas containingstream from a hydrocarbon or substituted hydrocarbon feed stream. Theapparatus further comprises, in addition to the WGS catalyst, a fuelreformer, a water gas shift reactor and a temperature controller.

The following described preferred embodiments of the WGS catalyst can beused in each one of the first, second, and third general embodiments orin specific, related embodiments (e.g., fuel cell reactors, fuelprocessors and hydrocarbon steam reformers.)

In a preferred embodiment, the Pt-free water gas shift catalystcomprises Ru, its oxides or mixtures thereof; Co, its oxides or mixturesthereof; and at least one of Zr, Ti, Eu, their oxides and mixturesthereof.

In another preferred embodiment, the water gas shift catalyst, with anessential absence of Pt, comprises Ru, its oxides or mixtures thereof;Co, its oxides or mixtures thereof; and at least one of Cr, Mo, Fe, La,Ce, their oxides and mixtures thereof.

In another preferred embodiment, the water gas shift catalyst, with anessential absence of Pt, comprises Ru, its oxides or mixtures thereof;Co, its oxides or mixtures thereof; and Mo, its oxides or mixturesthereof

In yet another preferred embodiment, the water gas shift catalyst,essential free of Pt, comprises Ru, its oxides or mixtures thereof; Co,its oxides or mixtures thereof; and at least one of Li, Na, K, Rb, Cs,Zr, their oxides and mixtures thereof. Particularly preferredembodiments include Ru, Co, Na, their oxides and mixtures thereof; Ru,Co, K, their oxides and mixtures thereof; and Ru, Co, Rb, their oxidesand mixtures thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

The patent or application file contains at least one drawing executed incolor. Copies of this patent or patent application publication withcolor drawing(s) will be provided by the Office upon request and paymentof the necessary fee.

The accompanying drawings, which are included to provide a furtherunderstanding of the invention and are incorporated in and constitute apart of this specification, illustrate preferred embodiments of theinvention and together with the detailed description serve to explainthe principles of the invention. In the drawings:

FIGS. 1A through 1C illustrate the process of producing a library testwafer.

FIGS. 2A and 2B illustrate the process of producing a library testwafer.

FIGS. 3A through 3G illustrate the process of producing a library testwafer and 3H through 3J illustrate SpotFire plots of the CO conversionversus CO₂ production for the wafer under WGS conditions at varioustemperatures. The legend for FIG. 3A also applies to FIGS. 3B through 3Gexclusively.

FIGS. 4A through 4C illustrate the process of producing a library testwafer and 4D through 4H illustrate SpotFire plots of the CO conversionversus CO₂ production for the wafer under WGS conditions at varioustemperatures.

FIGS. 5A through 5F illustrate the process of producing a library testwafer and 5G through 5I illustrate SpotFire plots of the CO conversionversus CO₂ production for the wafer under WGS conditions at varioustemperatures. The legend for FIG. 5A also applies to FIGS. 5B through 5Fexclusively.

FIG. 6 illustrates plots of CO concentration versus temperature forscaled-up catalyst samples under WGS conditions.

FIG. 7 illustrates plots of CO concentration versus temperature forscaled-up catalyst samples under WGS conditions.

FIG. 8 illustrates plots of CO concentration versus temperature forscaled-up catalyst samples under WGS conditions.

FIGS. 9A through 9F illustrate the compositional make-up of variousexemplary library test wafers. The legend for FIGS. 9A through C appliesonly to FIGS. 9A through C. The legend for FIGS. 9D through F appliesonly to FIGS. 9D through F.

FIG. 10A illustrates a representative plot of CO conversion versus CO2production for a prototypical library test wafer at varioustemperatures,

10B illustrates the effect of catalyst selectivity and activity versusthe WGS mass balance, and

10C illustrates the effect of temperature on catalyst performance underWGS conditions.

FIGS. 11A-11D illustrate plots of CO concentration versus temperaturefor scaled-up catalyst samples under WGS conditions.

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to a method for producing a hydrogen-rich gas,such as a hydrogen-rich syngas. According to the method a CO-containinggas, such as a syngas, contacts a water gas shift catalyst in thepresence of water, preferably a stoichiometric excess of water andpreferably at a reaction temperature of less than about 450° C., toproduce a hydrogen-rich gas, such as a hydrogen-rich syngas. Thereaction pressure is preferably not more than about 10 bar. Theinvention also relates to a water gas shift catalyst itself and toapparatus such as water gas shift reactors and fuel processing apparatuscomprising such WGS catalysts.

A water gas shift catalyst with an essential absence of Pt according tothe invention comprises:

-   -   (a) Ru, its oxides or mixtures thereof;    -   (b) Co, Mo, their oxides or mixtures thereof; and    -   (c) at least one of Li, Na, K, Rb, Cs, Ti, Zr, Cr, Fe, La, Ce,        Eu, their oxides and mixtures thereof. The WGS catalyst may be        supported on a carrier, such as any one member or a combination        of alumina, zirconia, titania, ceria, magnesia, lanthania,        niobia, zeolite, perovskite, silica clay, yttria and iron oxide.

The WGS catalysts of the invention comprise combinations of at leastthree metals or metalloids, selected from Ru, Co, Mo, and group c) asindicated above, in each and every possible permutation and combination,except as specifically and expressly excluded.

Discussion regarding the particular function of various components ofcatalysts and catalyst systems is provided herein solely to explain theadvantage of the invention, and is not limiting as to the scope of theinvention or the intended use, function, or mechanism of the variouscomponents and/or compositions disclosed and claimed. As such, anydiscussion of component and/or compositional function is made, withoutbeing bound by theory and by current understanding, unless and exceptsuch requirements are expressly recited in the claims. Generally, forexample, and without being bound by theory, ruthenium metal has activityas a WGS catalyst. Co, Mo and the group of metals comprised of Li, Na,K, Rb, Cs, Ti, Zr, Cr, Fe, La, Ce and Eu may themselves have activity asWGS catalysts but function in combination with Ru to impart beneficialproperties to the catalyst of the invention.

Catalysts of the invention can catalyze the WGS reaction at varyingtemperatures, avoid or attenuate unwanted side reactions such asmethanation reactions, as well as generate a hydrogen-rich gas, such asa hydrogen-rich syngas. The composition of the platinum-free WGScatalysts of the invention and their use in WGS reactions are discussedbelow.

1. Definitions

Water gas shift (WGS) reaction: Reaction which produces hydrogen andcarbon dioxide from water and carbon monoxide, and vice versa:H₂O+CO

H₂+CO₂

Generally, and unless explicitly stated to the contrary, each of the WGScatalysts of the invention can be advantageously applied both inconnection with the forward reaction as shown above (i.e., for theproduction of H₂), or alternatively, in connection with the reversereaction as shown above (i.e., for the production of CO). As such, thevarious catalysts disclosed herein can be used to specifically controlthe ratio of H₂ to CO in a gas stream.

Methanation reaction: Reaction which produces methane and water from acarbon source, such as carbon monoxide or carbon dioxide, and hydrogen:CO+3H₂→CH₄+H₂OCO₂+4H₂→CH₄+2H₂O

“Syngas” (also called synthesis gas): Gaseous mixture comprisinghydrogen (H₂) and carbon monoxide (CO) which may also contain other gascomponents such as carbon dioxide (CO₂), water (H₂O), methane (CH₄) andnitrogen (N₂).

LTS: Refers to “low temperature shift” reaction conditions where thereaction temperature is less than about 250° C., preferably ranging fromabout 150° C. to about 250° C.

MTS: Refers to “medium temperature shift” reaction conditions where thereaction temperature ranges from about 250° C. to about 350° C.

HTS: Refers to “high temperature shift” reaction conditions where thereaction temperature is more than about 350° C. and up to about 450° C.

Hydrocarbon: Compound containing hydrogen, carbon, and, optionally,oxygen.

The Periodic Table of the Elements is based on the present IUPACconvention, thus, for example, Group 9 comprises Co, Rh and Ir. (Seehttp://www.iupac.org dated May 30, 2002).

As discussed herein, the catalyst composition nomenclature uses a dash(i.e., “-”) to separate catalyst component groups where a catalyst maycontain one or more of the catalyst components listed for each componentgroup, brackets (i.e., “{ }”) are used to enclose the members of acatalyst component group, “{two of . . . }” is used if two or moremembers of a catalyst component group are required to be present in acatalyst composition, “blank” is used within the “{ }” to indicate thepossible choice that no additional element is added, and a slash (i.e.,“/”) is used to separate supported catalyst components from theirsupport material, if any. Additionally, the elements within a catalystcomposition formulation include all possible oxidation states, includingoxides, or salts, or mixtures thereof.

Using this shorthand nomenclature in this specification, for example,“Pt—{Rh, Ni}—{Na, K, Fe, Os}/ZrO₂” would represent catalyst compositionscontaining Pt, one or more of Rh and Ni, and one or more of Na, K, Fe,and Os supported on ZrO₂; all of the catalyst elements may be in anypossible oxidation state, unless explicitly indicated otherwise.“Pt—Rh—Ni—{two of Na, K, Fe, Os}” would represent a supported orunsupported catalyst composition containing Pt, Rh, and Ni, and two ormore of Na, K, Fe, and Os. “Ph—{Cu,Ag,Au}—{Na, K, blank}/TiO₂” wouldrepresent catalyst compositions containing Rh, one or more of Cu, Ag andAu, and, optionally, and one of Na or K supported on TiO₂.

The description of a catalyst composition formulation as having anessential absence of an element, or being “element-free” or“substantially element free” does allow for the presence of aninsignificant, non-functional amount of the specified element to bepresent, for example, as a non-functional impurity in a catalystcomposition formulation. However, such a description excludesformulations where the specific element has been intentionally orpurposefully added to the formulation to achieve a certain measurablebenefit. Typically, with respect to noble metals such as Pt for example,amounts less than about 0.01 weight percentage would not usually imparta material functional benefit with respect to catalyst performance, andtherefore such amounts would generally be considered as an insignificantamount, or not more than a mere impurity. In some embodiments, however,amounts up to less than about 0.04 weight percent may be includedwithout a material functional benefit to catalyst performance. In otherembodiments, amounts less than about 0.005 weight percent would beconsidered an insignificant amount, and therefore a non-functionalimpurity.

2. WGS Catalysts

A platinum-free water gas shift catalyst of the invention comprises:

-   -   (a) Ru, its oxides or mixtures thereof;    -   (b) Co, Mo, their oxides or mixtures thereof; and    -   (c) at least one of Li, Na, K, Rb, Cs, Ti, Zr, Cr, Fe, La, Ce,        Eu, their oxides and mixtures thereof. The catalyst components        are typically present in a mixture of the reduced or oxide        forms; typically one of the forms will predominate in the        mixture. The catalysts of the invention may be supported on        carriers. Suitable carriers for supported catalysts are        discussed below.

A WGS catalyst of the invention may be prepared by mixing the metalsand/or metalloids in their elemental forms or as oxides or salts to forma catalyst precursor. This catalyst precursor mixture generallyundergoes a calcination and/or reductive treatment, which may be in situ(within the reactor), prior to use as a WGS catalyst. Without beingbound by theory, the catalytically active species are generallyunderstood to be species which are in the reduced elemental state or inother possible higher oxidation states. The catalyst precursor speciesare believed to be substantially completely converted to thecatalytically active species by the pre-use treatment. Nonetheless, thecatalyst component species present after calcination and/or reductionmay be a mixture of catalytically active species such as the reducedmetal or other possible higher oxidation states and uncalcined orunreduced species depending on the efficiency of the calcination and/orreduction conditions.

A. Catalyst Compositions

As discussed above, one embodiment of the invention is a platinum-freecatalyst for catalyzing the water gas shift reaction (or its reversereaction). According to the invention, a WGS catalyst may have thefollowing composition:

-   -   (a) Ru, its oxides or mixtures thereof;    -   (b) Co, Mo, their oxides or mixtures thereof; and    -   (c) at least one of Li, Na, K, Rb, Cs, Ti, Zr, Cr, Fe, La, Ce,        Eu, their oxides and mixtures thereof.

The amount of each component present in a given catalyst according tothe present invention may vary depending on the reaction conditionsunder which the catalyst is intended to operate. Generally, theruthenium component may be present in an amount ranging from about 0.01wt. % to about 10 wt. %, preferably about 0.01 wt. % to about 2 wt. %,and more preferably about 0.05 wt. % to about 0.5 wt. %.

Cobalt may be present as either a bulk catalyst or a supported catalystcomposition. Bulk cobalt catalysts may have Co concentration rangingfrom a high of about 90% to a low of about 30%, preferred is about 40%to about 70%; generally a bulk cobalt catalyst may contain about 10 wt.% binder. Bulk cobalt catalysts may also contain other components suchas zirconium, magnesium, silicon or aluminum. Supported cobalt catalystsmay have Co concentrations ranging from about 0.05% up to about 25 wt. %Co, with about 0.10% to about 15% a preferred range for Coconcentration.

The lanthanide elements and transition metals may be present, typically,in amounts ranging from about 0.05 wt. % to about 20 wt. %, preferablyabout 0.1 wt. % to about 15 wt. %. The main group and metalloid elementsmay be present in amounts ranging, generally, from about 0.01 wt. % toabout 15 wt. %, preferably about 0.02 wt. % to about 10 wt. %.

The above weight percentages are calculated on the total weight of thecatalyst component, in its final state in the catalyst composition afterthe final catalyst preparation step (i.e., the resulting oxidation stateor states) with respect to the total weight of all catalyst componentsplus the support material, if any. The presence of a given catalystcomponent in the support material and the extent and type of itsinteraction with other catalyst components may effect the amount of acomponent needed to achieve the desired performance effect.

In a preferred embodiment, the platinum-free water gas shift catalyst ofthe invention comprises Ru, Co and at least one of Zr, Ti and Eu.

In another preferred embodiment, the platinum-free water gas shiftcatalyst comprises Ru, Co and at least one of Cr, Mo, Fe, La and Ce. Ina particularly preferred embodiment, the platinum-free water gas shiftcatalyst comprises Ru, Co, Fe and at least one of Cr, La and Ce. Inanother particularly preferred embodiment, the platinum-free catalystcomprises Ru, Co and Fe. Another particularly preferred embodimentincludes Ru—Co—Fe—{Na, K}.

In yet another preferred embodiment, the platinum-free water gas shiftcatalyst comprises Ru and Co, at least one of Li, Na, K, Rb, Cs and Zr.Particularly preferred embodiments include Ru—Co—{Na, K, Rb} andRu—Co—Na—Li.

In another preferred embodiment, the platinum-free water gas shiftcatalyst comprises Ru, Co, and Mo.

The catalysts may be more advantageously applied in specific operatingtemperature ranges. For instance, addition of alkali metals to the Ru—Cocore significantly enhances the LTS and MTS activity of the supported orunsupported catalysts. A preferred alkali metal is Na for LTS and Na orK for MTS. Ru—Co—Na catalyst compositions maintain their high LTS andMTS activity on any support. Exemplary supports include not onlyzirconia, titania, bulk Co and ceria but also less expensive silicas andaluminas. One preferred embodiment is Ru and/or Na, K and Rb supportedon bulk Co. A particularly preferred supported catalyst composition forLTS and MTS activity is sodium hydroxide promoted Ru—Co/ZrO₂ wheresodium hydroxide is a precursor that provides the source of Na.

B. Catalyst Components a) and b): Ru and Co

Ru, its oxides or mixtures thereof and Co, its oxides or mixturesthereof are required metal components in a catalyst composition of theinvention. Ru and Co may be present in an independent combination oftheir reduced forms and their oxides.

Unmodified Ru has been shown to catalyze the WGS reaction and is moreactive and less selective than Pt. Co is an example of a performanceadditive for Ru, along with the other components of the invention. Comay be present in the WGS catalyst compositions of the invention in abulk state.

C. Catalyst Component c): Components Other than Ru and Co

The platinum-free WGS catalysts of the invention contain at least threemetals or metalloids. In addition to the Ru and Co components discussedabove, the catalyst contains metals or metalloids which, when used incombination with Ru and Co, function to impart beneficial properties tothe catalyst of the invention. A catalyst of the invention, then,further comprises at least one of Li, Na, K, Rb, Cs, Ti, Zr, Cr, Mo, Fe,La, Ce, Eu, their oxides and mixtures thereof.

D. Functional Classification of Catalyst Components

Without limiting the scope of the invention, discussion of the functionsof the various catalyst components is offered, along with a template forcomposing catalyst compositions according to the invention. Thefollowing classification of catalyst components will direct one of skillin the art in the selection of various catalyst components to formulateWGS catalyst compositions according to the present invention anddepending on the reaction conditions of interest.

Furthermore, there are several metals which may be incorporated into awater gas shift catalyst according to the invention. Hence, the variouselements recited as components in any of the described embodiments maybe included in any various combination and permutation to achieve acatalyst composition that is coarsely or finely tuned for a specificapplication (e.g., including for a specific set of conditions, such as,temperature, pressure, space velocity, catalyst precursor, catalystloading, catalyst surface area/presentation, reactant flow rates,reactant ratios, etc.). In some cases, the effect of a given componentmay vary with the operating temperature for the catalyst. These catalystcomponents may function as, for instance, activators or moderatorsdepending upon their effect on the performance characteristics of thecatalyst. For example, if greater activity is desired, an activator maybe incorporated into a catalyst, or a moderator may be replaced by atleast one activator or, alternatively, by at least one moderator onestep further up the “activity ladder.” An “activity ladder” rankssecondary or added catalyst components, such as activators ormoderators, in order of the magnitude of their respective effect on theperformance of a principal catalyst constituent. Conversely, if WGSselectivity of a catalyst needs to be increased (e.g., decrease theoccurrence of the competing methanation reaction), then either anactivator may be removed from the catalyst or, alternatively, thecurrent moderator may be replaced by at least one moderator one stepdown the “activity ladder.” The function of these catalyst componentsmay be further described as “hard” or “soft” depending on the relativeeffect obtained by incorporating a given component into a catalyst. Thecatalyst components may be metals, metalloids, or non-metals.

As an example, the undoped combination of Ru and Co results in an activebut unselective WGS catalyst at higher temperatures. Doping with amoderator of at least one of Na, K and Rb dramatically enhancesselectivity of the catalyst such that the LTS and MTS selectivityapproaches or surpasses Pt/ZrO₂, especially at higher temperatures. Ofthe doping metals, Na is the most active and efficient at LTS but K andRb are the most selective at MTS. Additional Zr doping is expected tofurther enhance performance.

An example of another embodiment of a WGS catalyst of the invention isRu—Co—Fe. The Ru—Co—Fe catalyst exhibits synergistic properties and canbe used as a bulk catalyst (e.g., precipitated CoFe optionally dopedwith other metals) or supported on conventional carriers such aszirconia, titania or ceria. At LTS and MTS, Fe acts an efficientselectivity-enhancing moderator to the otherwise too active andunselective Ru and Co combination. At higher temperatures, however, Febecomes active on its own and therefore adds to overall activity of theRu—Co—Fe ternary. High surface areas can be achieved by supporting theRu—Co—Fe catalyst on conventional carriers such as, for example,zirconia and/or by adding stabilizing components such as, for example,Cr, La and Ce.

According to the present invention Ru and Co are active and selectiveWGS-promoting metals. The Ru—Co combination may be activated byactivators which include, but are not limited to, Li, Na, K, Rb, Ti, Zrand Ce. Ce may be the most active rare earth metal for activating theWGS reaction. La and Eu may also be active, particularly at lowertemperatures. In general, all lanthanides, other than Ce, showcomparable performance and tend to moderate rather than activate noblemetal containing catalyst systems. La is only slightly moderating whendoping Ce and may therefore be used to adjust the selectivity of Cecontaining catalyst systems. Fe is an example of a selective activatorover a broad dynamic range.

E. Supports

The support or carrier may be any support or carrier used with thecatalyst which allows the water gas shift reaction to proceed. Thesupport or carrier may be a porous, adsorptive, high surface areasupport with a surface area of about 25 to about 500 m²/g. The porouscarrier material may be relatively inert to the conditions utilized inthe WGS process, and may include carrier materials that havetraditionally be utilized in hydrocarbon steam reforming processes, suchas, (1) activated carbon, coke, or charcoal; (2) silica or silica gel,silicon carbide, clays, and silicates including those syntheticallyprepared and naturally occurring, for example, china clay, diatomaceousearth, fuller's earth, kaolin, etc.; (3) ceramics, porcelain, bauxite;(4) refractory inorganic oxides such as alumina, titanium dioxide,zirconium oxide, magnesia, etc.; (5) crystalline and amorphousaluminosilicates such as naturally occurring or synthetically preparedmordenite and/or faujasite; and, (6) combinations of these groups.

When a WGS catalyst of the invention is a supported catalyst, thesupport utilized may contain one or more of the metals (or metalloids)of the catalyst. The support may contain sufficient or excess amounts ofthe metal for the catalyst such that the catalyst may be formed bycombining the other components with the support. Examples of suchsupports include ceria which can contribute cerium, Ce, to a catalyst oriron oxide which can contribute iron, Fe. When such supports are used,the amount of the catalyst component in the support typically may be farin excess of the amount of the catalyst component needed for thecatalyst. Thus the support may act as both an active catalyst componentand a support material for the catalyst. Alternatively, the support mayhave only minor amounts of a metal making up the WGS catalyst such thatthe catalyst may be formed by combining all desired components on thesupport.

Carrier screening with Pt as the only active noble metal revealed that awater gas shift catalyst may also be supported on a carrier comprisingalumina, zirconia, titania, ceria, magnesia, lanthania, niobia, zeolite,perovskite, silica clay, yttria and iron oxide. Perovskite as well assupported perovskites (e.g., supported on any of the previously listedcarriers) may also be utilized as a support for the inventive catalystformulations.

Zirconia, titania and ceria may be supports for the present inventionand provide high activity for the WGS reaction. Niobia, yttria and ironoxide carriers provide high selectivity but are also less active whichis believed to be due to a lack of surface area. In addition to theiruse as carriers, iron, yttrium and magnesium oxides may be utilized asprimary layers on zirconia carriers to provide both higher surface areaand low moderator concentration.

In general, alumina has been found to be an active but unselectivecarrier for Pt only containing WGS catalysts. However, the selectivityof gamma alumina may be improved by doping with Zr, Co, or one of therare earth elements, such as, for example, La and Ce alone or incombination. This doping may be accomplished by addition of the oxidesor other salts such as nitrates, in either liquid or solid form, to thealumina. Other possible dopants to increase the selectivity includeredox dopants, such as for instance, Re, Mo, Fe, and basic dopants.Preferred is an embodiment of gamma alumina combined with Zr and/or Cowhich exhibits both high activity and selectivity over a broadtemperature range.

High surface area aluminas, such as gamma-, delta- or theta-alumina arepreferred alumina carriers. Other alumina carriers, such as mixed silicaalumina, sol-gel alumina, and sol-gel or coprecipitated alumina-zirconiacarriers may be used. Alumina typically has a higher surface area and ahigher pore volume than carriers such as zirconia and usually offers aprice advantage over other more expensive carriers.

Zirconia is a preferred carrier for use with the WGS catalysts of theinvention. Monoclinic zirconia is particularly preferred. When zirconia,particularly monoclinic zirconia, is used as the catalyst carrier, theresulting catalyst compositions have shown enhanced activity under LTSconditions. That is in contrast with other carriers such as gammaalumina. This carrier effect is less pronounced for catalysts containingNa in view of Na tending to cover the surface of the carrier.

Examples of a carrier supported platinum-free WGS catalyst of theinvention include: Ru—Co—{Zr, Eu, Mo, Fe, Na}/γ-Al₂O₃, particularlyRu—Co—Zr/γ-Al₂O₃; Ru—Co—Eu/γ-Al₂O₃; Ru—Co—Mo/γ-Al₂O₃; Ru—Co—Fe/γ-Al₂O₃;and Ru—Co—Na/γ-Al₂O₃; and

-   -   Ru—Co—{Eu, Mo, Fe, Na, blank}/ZrO₂; particularly Ru—Co—Eu/ZrO₂;        Ru—Co—Mo/ZrO₂; Ru—Co—Fe/ZrO₂; Ru—Co—Na/ZrO₂; Ru—Co/ZrO₂;        Ru—Co—Fe—{Na, K}/ZrO₂ and Ru—Co—Fe—{Na, K, Zr}/γ-Al₂O₃.

F. Methods of Making a WGS Catalyst

As set forth above, a platinum-free WGS catalyst of the invention may beprepared by mixing the metals and/or metalloids in their elemental formsor as oxides or salts to form a catalyst precursor, which generallyundergoes a calcination and/or reductive treatment. Without being boundby theory, the catalytically active species are generally understood tobe species which are in the reduced elemental state or in other possiblehigher oxidation states.

The WGS catalysts of the invention may be prepared by any well knowncatalyst synthesis processes. See, for example, U.S. Pat. Nos. 6,299,995and 6,293,979. Spray drying, precipitation, impregnation, incipientwetness, ion exchange, fluid bed coating, physical or chemical vapordeposition are just examples of several methods that may be utilized tomake the present WGS catalysts. Preferred approaches, include, forinstance, impregnation or incipient wetness. The catalyst may be in anysuitable form, such as, pellets, granular, bed, or monolith. See alsothe co-pending U.S. patent application Ser. No. 10/739,428 listingHagemeyer et al., and filed on Dec. 18, 2003under for further details onmethods of catalyst preparation and catalyst precursors.

The WGS catalyst of the invention may be prepared on a solid support orcarrier material. Preferably, the support or carrier is, or is coatedwith, a high surface area material onto which the precursors of thecatalyst are added by any of several different possible techniques, asset forth above and as known in the art. The catalyst of the inventionmay be employed in the form of pellets, or on a support, preferably amonolith, for instance a honeycomb monolith.

Catalyst precursor solutions are preferably composed of easilydecomposable forms of the catalyst component in a sufficiently highenough concentration to permit convenient preparation. Examples ofeasily decomposable precursor forms include the nitrate, amine, andoxalate salts. Typically chlorine containing precursors are avoided toprevent chlorine poisoning of the catalyst. Solutions can be aqueous ornon-aqueous solutions. Exemplary non-aqueous solvents can include polarsolvents, aprotic solvents, alcohols, and crown ethers, for example,tetrahydrofuran and ethanol. Concentration of the precursor solutionsgenerally may be up to the solubility limitations of the preparationtechnique with consideration given to such parameters as, for example,porosity of the support, number of impregnation steps, pH of theprecursor solutions, and so forth. The appropriate catalyst componentprecursor concentration can be readily determined by one of ordinaryskill in the art of catalyst preparation.

Li—The acetate, hydroxide, nitrate and formate salts are both possiblecatalyst precursors for lithium.

Na—Sodium acetate, alkoxides including methoxide, propoxide, andethoxide, bicarbonate, carbonate, citrate, formate, hydroxide, nitrate,nitrite and oxalate may be used to prepare WGS catalysts of theinvention.

Mg—Water soluble magnesium precursors include the nitrate, acetate,lactate and formate salts.

K—Potassium nitrate, acetate, carbonate, hydroxide and formate arepossible potassium catalyst precursors. The KOAc salt is volatile withpossible potassium losses when heating up to calcination temperature.

Ca—The nitrate, acetate and hydroxide salts, preferable salts highlysoluble in water, may be used to prepare catalysts of the invention.

Sc—The nitrate salt, Sc(NO₃)₃ may be a precursor for scandium.

Ti—Titanium precursors which may be utilized in the present inventioninclude ammonium titanyl oxalate, (NH₄)₂TiO(C₂O₄)₂, available fromAldrich, and titanium(IV) bis(ammonium lactato)dihydroxide, 50 wt. %solution in water,

[CH₃CH(O—)CO₂NH₄]₂Ti(OH)₂, available from Aldrich. Other titaniumcontaining precursors include Ti oxalate prepared by dissolving a Ti(IV)alkoxide, such as Ti(IV) propoxide, Ti(OCH₂CH₂CH₃)₄, (Aldrich) in 1Maqueous oxalic acid at 60° C. and stirring for a couple of hours, toproduce a 0.72M clear colorless solution; TiO(acac)oxalate prepared bydissolving Ti(IV) oxide acetylacetonate, TiO(acac)₂, (Aldrich) in 1.5Maqueous oxalic acid at 60° C. with stirring for a couple of hours,following by cooling to room temperature overnight to produce 1M clearyellow-brown solution; TiO(acac)₂, may also be dissolved in diluteacetic acid (50:50 HOAc:H₂O) at room temperature to produce a 1M clearyellow solution of TiO-acac. Preferably, titanium dioxide in the anataseform is utilized as a catalyst precursor material.

V—Vanadium (IV) oxalate, a vanadium precursor, may be prepared fromV₂O₅, (Aldrich), which is slurried in 1.5M aqueous oxalic acid on hotplate for 1 hour until it turns dark blue due to V(V) reduction to V(IV)by oxalic acid. Ammonium metavanadate(V), (NH₄)VO₃, (Cerac, Alfa) may beused as a precursor by dissolving it in water, preferably hot, about 80°C. water. Various polycarboxylic organic acid vanadium precursors can beprepared and used as catalyst precursors, for example, citric, maleic,malonic, and tatartic. Vanadium citrate can be prepared by reacting V₂O₅with citric acid, and heating to about 80° C. Ammonium vanadium(V)oxalate may be prepared by reacting (NH₄)VO₃ and NH₄OH in roomtemperature water, increasing temperature to 90° C., stirring todissolve all solids, cooling to room temperature and adding oxalic acid;this produces a clear orange solution, which is stable for about 2 days.Ammonium vanadium(V) citrate and ammonium vanadium(V) lactate are bothprepared by shaking NH₄VO₃ in, respectively, aqueous citric acid oraqueous lactic acid, at room temperature. Diammonium vanadium(V) citratemay be prepared by dissolving, for instance, 0.25M NH₄VO₃ in citric aciddiammonium salt (Alfa) at room temperature. An exemplary method ofpreparing ammonium vanadium(V) formate is to dissolve NH₄VO₃ (0.25M) inwater at 95° C., react with 98% formic acid and NH₄OH to produce thedesired ammonium vanadium(V) formate.

Cr—Both the nitrate and acetate hydroxides are possible catalystprecursors for chromium.

Mn—Manganese nitrate, manganese acetate (Aldrich) and manganese formate(Alfa) are all possible catalyst precursors for manganese.

Fe—Iron (III) nitrate, Fe(NO₃)₃, iron(III) ammonium oxalate,(NH₄)₃Fe(C₂O₄)₃, iron(III) oxalate, Fe₂(C₂O₄)₃, and iron(II) acetate,Fe(OAc)₂, are all water soluble; although the iron(III)oxalate undergoesthermal decomposition at only 100° C. Potassium iron(III) oxalate,iron(III) formate and iron(III) citrate are additional iron precursors.

Co—Both cobalt nitrate and acetate are water soluble precursorsolutions. The cobalt (II) formate, Co(OOCH)₂, has low solubility incold water of about 5 g/100 mL, while cobalt (II) oxalate is soluble inaqueous NH₄OH. Another possible precursor is sodiumhexanitrocobaltate(III), Na₃Co(NO₂)₆ which is water soluble, withgradual decomposition of aqueous solutions slowed by addition of smallamounts of acetic acid. Hexaammine Co(III) nitrate is also soluble inhot (65° C.) water and NMe₄OH. Cobalt citrate, prepared by dissolvingCo(OH)₂ in aqueous citric acid at 80° C. for 1 to 2 hours, is anothersuitable cobalt precursor.

Ni—Nickel nitrate, Ni(NO₃)₂, and nickel formate are both possible nickelprecursors. The nickel formate may be prepared by dissolving Ni(HCO₂)₂in water and adding formic acid, or by dissolving in dilute formic acid,to produce clear greenish solutions. Nickel acetate, Ni(OAc)₂, is also anickel precursor. Nickel chloride, NiCl₂, may also be used whenprecipitating nickel salts such as nickel hydroxide or nickel carbonate.In contrast to catalyst compositions containing noble metals, base metalcatalysts, such as bulk Ni, are not poisoned by chloride.

Cu—Copper precursors include nitrate, Cu(NO₃)₂, acetate, Cu(OAc)₂, andformate, Cu(OOCH)₂, which are increasingly less water soluble in theorder presented. Ammonium hydroxide is used to solublize oxalate,Cu(C₂O₄)₂, and Cu(NH₃)₄(OH)₂ which is soluble in aqueous 5N NH₄OH.Copper citrate and copper amine carbonate may be prepared from Cu(OH)₂.

Zn—Zinc nitrate, acetate and formate are all water soluble and possiblecatalyst precursors. Ammonium zinc carbonate, (NH₄)₂Zn(OH)₂CO₃, preparedby reacting zinc hydroxide and ammonium carbonate for a week at roomtemperature, is another possible precursor for zinc.

Ge—Germanium oxalate may be prepared from amorphous Ge(IV) oxide,glycol-soluble GeO₂, (Aldrich) by reaction with 1M aqueous oxalic acidat room temperature. H₂GeO₃ may be prepared by dissolving GeO₂ in waterat 80° C. and adding 3 drops of NH₄OH (25%) to produce a clear,colorless H₂GeO₃ solution. (NMe₄)₂GeO₃ may be prepared by dissolving0.25M GeO₂ in 0.1 M NMe₄OH. (NH₄)₂GeO₃ may be prepared by dissolving0.25M GeO₂ in 0.25M NH₄OH.

Rb—The nitrate, acetate, carbonate and hydroxide salts may be used ascatalyst precursors to prepare the WGS catalyst of the invention.Preferred are water soluble salts.

Sr—The acetate is soluble in cold water to produce a clear colorlesssolution.

Y—Yttrium nitrate and acetate are both possible catalyst precursors.

Zr—Zirconyl nitrate and acetate, commercially available from Aldrich,and ammonium Zr carbonate and zirconia, available from MEI, are possibleprecursors for zirconium in either or both the support or catalystformulation itself.

Nb—Niobium oxalate prepared by dissolving niobium (V) ethoxide inaqueous oxalic acid at 60° C. for 12 hours is a possible catalystprecursor. Another preparative route to the oxalate is dissolving niobicacid or niobic oxide (Nb₂O₅) in oxalic acid at 65° C. Ammonium Nboxalate is also a possible catalyst precursor for niobium. Dissolvingniobic oxide (0.10M Nb) in NMe₄OH (0.25M) and stirring overnight at 65°C. will produce (NMe₄)₂NbO₆.

Mo—Molybdenum containing precursor solutions may be derived fromammonium molybdate (NH₄)₂MoO₄ (Aldrich) dissolved in room temperaturewater; Mo oxalate prepared by dissolving MoO₃ (Aldrich) in 1.5M aqueousoxalic acid at 60° C. overnight; and ammonium Mo oxalate prepared from(NH₄)₆Mo₇O₂₄.4H₂O (Strem) dissolved in 1M aqueous oxalic acid at roomtemperature. (NH₄)₆Mo₇O₂₄.4H₂O (Strem) may also be dissolved in water atroom temperature to produce a stable solution of ammonium paramolybdatetetrahydrate. Molybdic acid, H₂MoO₄, (Alfa Aesar or Aldrich) may each bedissolved in room temperature water to produce 1M Mo containingsolutions.

Ru—Ru nitrosyl nitrate, Ru(NO)(NO₃)₃ (Aldrich), potassium rutheniumoxide, K₂RuO₄.H₂O, potassium perruthenate, KRuO₄, ruthenium nitrosylacetate, Ru(NO)(OAc)₃, and tetrabutylammonium perruthenate, NBu4RuO₄,are all possible ruthenium metal catalyst precursors. NMe₄Ru(NO)(OH)₄solution can be prepared by dissolving Ru(NO)(OH)₃ (0.1M) (H.C. Starck)in NMe4OH (0.12M) at 80° C. produces a clear dark red-brown 0.1M Rusolution useful as a catalyst precursor solution.

Rh—A suitable rhodium catalyst precursor is Rh nitrate (Aldrich orStrem).

Pd—Catalyst compositions containing Pd can be prepared by usingprecursors like Pd nitrate, typically stabilized by dilute HNO₃, andavailable as a 10 wt. % solution from Aldrich, or Pd(NH₃)₂(NO₂)₂available as a 5 wt. % Pd commercial solution, stabilized by diluteNH₄OH. Pd(NH₃)₄(NO₃)₂ and Pd(NH₃)₄(OH)₂ are also available commercially.

Ag—Silver nitrate, silver nitrite, silver diammine nitrite, and silveracetate are possible silver catalyst precursors.

Cd—Cadmium nitrate is water soluble and a suitable catalyst precursor.

In—Indium formate and indium nitrate are preferred precursors forindium.

Sn—Tin oxalate produced by reacting the acetate with oxalic acid may beused as a catalyst precursor. Tin tartrate, SnC₄H₄O₆, in NMe₄OH at about0.25M Sn concentration, and tin acetate, also dissolved in NMe₄OH atabout 0.25M Sn concentration, may be used as catalyst precursors.

Sb—Ammonium antimony oxalate produced by reacting the acetate withoxalic acid and ammonia is a suitable antimony precursor. Antimonyoxalate, Sb₂(C₂O₄)₃, available from Pfaltz & Bauer, is a water solubleprecursor. Potassium antimony oxide, KSbO₃, and antimony citrate,prepared by stirring antimony(II) acetate in 1M citric acid at roomtemperature, are both possible catalyst precursors.

Te—Telluric acid, Te(OH)₆, may be used as a precursor for tellurium.

Cs—Cs salts including the nitrate, acetate, carbonate, and hydroxide aresoluble in water and possible catalyst precursors.

Ba—Barium acetate and barium nitrate are both suitable precursors forbarium catalyst components.

La—Lanthanum precursors include nitrate, La(NO₃)₃, acetate, La(OAc)₃,and perchlorate, La(ClO₄)₃, all of which may be prepared as aqueoussolutions.

Ce—Ce(III) and Ce(IV) solutions may be prepared from Ce(III) nitratehexahydrate, Ce(NO₃)₃.6H₂O, (Aldrich) and ammonium cerium(IV) nitrate,(NH₄)₂Ce(NO₃)₆, (Aldrich), respectively, by dissolution in roomtemperature water. Nitric acid, 5 vol. %, may be added to the Ce(III)salt to increase solubility and stability. Ce(OAc)₃ (Alfa) or Ce(NO₃)₄(Alfa) may also be utilized as a catalyst precursor.

Pr, Nd, Sm and Eu—The nitrate, Ln(NO₃)₃, or acetate, Ln(O₂CCH₃)₃, arepossible catalyst precursors for these lanthanides.

Hf—Hafnoyl chloride and nitrate are both possible precursors. Preparingthe hafnoyl nitrate by dissolving Hf(acac)₄ in dilute HNO₃ at low heatprovides a clear stable solution of hafnoyl nitrate.

Ta—Tantalum oxalate solution, Ta₂O(C₂O₄)₄, available from H. C. Starck,or prepared by dissolving Ta(OEt)₅ in aqueous oxalic acid at 60° C. for12 hours, is a possible catalyst precursor.

W—Ammonium metatungstate hydrate, (NH₄)₆W₁₂O₃₉, is water soluble and apossible tungsten catalyst precursor. H₂WO₄ is reacted with NH₄OH andNMe₄OH, respectively, to prepare (NH₄)₂WO₄ and (NMe₄)₂WO₄ which are bothpossible precursors.

Re—Rhenium oxide in H₂O₂, perrhenic acid, (HReO₄), NaReO₄ and NH₄ReO₄are suitable rhenium precursors.

Ir—Hexachloroiridate acid, H₂IrCl₆, potassium hexacyanoiridate andpotassium hexanitroiridate are all possible catalyst precursors foriridium.

Pt—Platinum containing catalyst compositions may be prepared by usingany one of a number of precursor solutions, such as, Pt(NH₃)₄(NO₃)₂(Aldrich, Alfa, Heraeus, or Strem), Pt(NH₃)₂(NO₂)₂ in nitric acid,Pt(NH₃)₄(OH)₂ (Alfa), K₂Pt(NO₂)₄, Pt(NO₃)₂, PtCl₄ and H₂PtCl₆(chloroplatinic acid). Pt(NH₃)₄(HCO₃)₂, Pt(NH₃)₄(HPO₄), (NMe₄)₂Pt(OH)₆,H₂Pt(OH)₆, K₂Pt(OH)₆, Na₂Pt(OH)₆ and K₂Pt(CN)₆ are also possible choicesalong with Pt oxalate salts, such as K₂Pt(C₂O₄)₂. The Pt oxalate saltsmay be prepared from Pt(NH₃)₄(OH)₂ which is reacted with 1M oxalic acidsolution to produce a clear, colorless solution of the desired Ptoxalate salts.

Au—Auric acid, HAuCl₄, in dilute HCl at about 5% Au may be a goldprecursor. Gold nitrate in 0.1M concentration may be prepared bydissolving HAu(NO₃)₄ (Alfa) in concentrated nitric acid, followed bystirring at room temperature for 1 week in the dark, then diluting 1:1with water to produce a yellow solution. It should be noted that furtherdilution may result in Au precipitation. More concentrated, 0.25M, forexample, gold nitrate may be prepared by starting with Au(OH)₃ (Alfa).NaAu(OH)₄, KAu(OH)₄, and NMe₄Au(OH)₄ may each be prepared from Au(OH)₃dissolved in bases NaOH, KOH, or NMe₄OH, respectively, in baseconcentrations ranging from, for instance, 0.25M or higher.

3. Producing a Hydrogen-Rich Gas, such as, a Hydrogen-Rich Syngas

The invention also relates to a method for producing a hydrogen-richgas, such as, a hydrogen-rich syngas. An additional embodiment of theinvention may be directed to a method of producing a CO-depleted gas,such as a CO-depleted syngas.

A CO-containing gas, such as a syngas, contacts with a water gas shiftcatalyst in the presence of water according to the method of theinvention. The reaction preferably may occur at a temperature of lessthan 450° C. to produce a hydrogen-rich gas, such as a hydrogen-richsyngas.

A method of the invention may be utilized over a broad range of reactionconditions. Preferably, the method is conducted at a pressure of no morethan about 75 bar, preferably at a pressure of no more than about 50 barto produce a hydrogen-rich syngas. Even more preferred is to have thereaction occur at a pressure of no more than about 25 bar, or even nomore than about 15 bar, or not more than about 10 bar. Especiallypreferred is to have the reaction occur at, or about atmosphericpressure. Depending on the formulation of the catalyst according to thepresent invention, the present method may be conducted at reactant gastemperatures ranging from less than about 250° C. to up to about 450° C.Preferably, the reaction occurs at a temperature selected from one ormore temperature subranges of LTS, MTS and/or HTS as described above.Space velocities may range from about 1 hr⁻¹ up to about 1,000,000 hr⁻¹.Feed ratios, temperature, pressure and the desired product ratio arefactors that would normally be considered by one of skill in the art todetermine a desired optimum space velocity for a particular catalystformulation.

4. Fuel Processor Apparatus

The invention further relates to a fuel processing system for generationof a hydrogen-rich gas from a hydrocarbon or substituted hydrocarbonfuel. Such a fuel processing system would comprise, for example, a fuelreformer, a water gas shift reactor and a temperature controller.

The fuel reformer would convert a fuel reactant stream comprising ahydrocarbon or a substituted hydrocarbon fuel to a reformed productstream comprising carbon monoxide and water. The fuel reformer maytypically have an inlet for receiving the reactant stream, a reactionchamber for converting the reactant stream to the product stream, and anoutlet for discharging the product stream.

The fuel processor system would also comprise a water gas shift reactorfor effecting a water gas shift reaction at a temperature of less thanabout 450° C. This water gas shift reactor may comprise an inlet forreceiving a water gas shift feed stream comprising carbon monoxide andwater from the product stream of the fuel reformer, a reaction chamberhaving a water gas shift catalyst as described herein located therein,and an outlet for discharging the resulting hydrogen-rich gas. The watergas shift catalyst would preferable be effective for generating hydrogenand carbon dioxide from the water gas shift feed stream.

The temperature controller may be adapted to maintain the temperature ofthe reaction chamber of the water gas shift reactor at a temperature ofless than about 450° C.

5. Industrial Applications

Syngas is used as a reactant feed in number of industrial applications,including for example, methanol synthesis, ammonia synthesis,oxoaldehyde synthesis from olefins (typically in combination with asubsequent hydrogenation to form the corresponding oxoalcohol),hydrogenations and carbonylations. Each of these various industrialapplications preferably includes a certain ratio of H₂ to CO in thesyngas reactant stream. For methanol synthesis the ratio of H₂:CO ispreferably about 2:1. For oxosynthesis of oxoaldehydes from olefins, theratio of H₂:CO is preferably about 1:1. For ammonia synthesis, the ratioof H₂ to N₂ (e.g., supplied from air) is preferably about 3:1. Forhydrogenations, syngas feed streams that have higher ratios of H₂:CO arepreferred (e.g., feed streams that are H₂ enriched, and that arepreferably substantially H₂ pure feed streams). Carbonylation reactionsare preferably effected using feed streams that have lower ratios ofH₂:CO (e.g., feed streams that are CO enriched, and that are preferablysubstantially CO pure feed streams).

The WGS catalysts of the present invention, and the methods disclosedherein that employ such WGS catalysts, can be applied industrially toadjust or control the relative ratio H₂:CO in a feed stream for asynthesis reaction, such as methanol synthesis, ammonia synthesis,oxoaldehyde synthesis, hydrogenation reactions and carbonylationreactions. In one embodiment, for example, a syngas product streamcomprising CO and H₂ can be produced from a hydrocarbon by a reformingreaction in a reformer (e.g., by steam reforming of a hydrocarbon suchas methanol or naphtha). The syngas product stream can then be fed(directly or indirectly after further downstream processing) as the feedstream to a WGS reactor, preferably having a temperature controlleradapted to maintain the temperature of the WGS reactor at a temperatureof about 450° C. or less during the WGS reaction (or at lowertemperatures or temperature ranges as described herein in connectionwith the catalysts of the present invention). The WGS catalyst(s)employed in the WGS reactor are preferably selected from one or more ofthe catalysts and/or methods of the invention. The feed stream to theWGS reactor is contacted with the WGS catalyst(s) under reactionconditions effective for controlling the ratio of H₂:CO in the productstream from the WGS reactor (i.e., the “shifted product stream”) to thedesired ratio for the downstream reaction of interest (e.g., methanolsynthesis), including to ratios described above in connection with thevarious reactions of industrial significance. As a non-limiting example,a syngas product stream from a methane steam reformer will typicallyhave a H₂:CO ratio of about 6:1. The WGS catalyst(s) of the presentinvention can be employed in a WGS reaction (in the forward direction asshown above) to further enhance the amount of H₂ relative to CO, forexample to more than about 10:1for a downstream hydrogenation reaction.As another example, the ratio of H₂:CO in such a syngas product streamcan be reduced by using a WGS catalyst(s) of the present invention in aWGS reaction (in the reverse direction as shown above) to achieve orapproach the desired 2:1 ratio for methanol synthesis. Other exampleswill be known to a person of skill in the art in view of the teachingsof the present invention.

A person of skill in the art will understand and appreciate that withrespect to each of the preferred catalyst embodiments as described inthe preceding paragraphs, the particular components of each embodimentcan be present in their elemental state, or in one or more oxide states,or mixtures thereof.

Although the foregoing description is directed to the preferredembodiments of the invention, it is noted that other variations andmodifications will be apparent to those skilled in the art, and whichmay be made without departing from the spirit or scope of the invention.

EXAMPLES

General

Small quantity catalyst composition samples are generally prepared byautomated liquid dispensing robots (Cavro Scientific Instruments) onflat quartz test wafers.

Generally, supported catalysts are prepared by providing a catalystsupport (e.g. alumina, silica, titania, etc.) to the wafer substrate,typically as a slurry composition using a liquid-handling robot toindividual regions or locations on the substrate or by wash-coating asurface of the substrate using techniques known to those of skill in theart, and drying to form dried solid support material on the substrate.Discrete regions of the support-containing substrate are thenimpregnated with specified compositions intended to operate as catalystsor catalyst precursors, with the compositions comprising metals (e.g.various combinations of transition metal salts). In some circumstancesthe compositions are delivered to the region as a mixture of differentmetal-containing components and in some circumstances (additionally oralternatively) repeated or repetitive impregnation steps are performedusing different metal-containing precursors. The compositions are driedto form supported catalyst precursors. The supported catalyst precursorsare treated by calcining and/or reducing to form active supportedcatalytic materials at discrete regions on the wafer substrate.

Bulk catalysts (e.g. noble-metal-free Co-containing catalysts) may alsobe prepared on the substrate. Such multi-component bulk catalysts arepurchased from a commercial source and/or are prepared by precipitationor co-precipitation protocols, and then optionally treated—includingmechanical pretreatment (grinding, sieving, pressing). The bulkcatalysts are placed on the substrate, typically by slurry dispensingand drying, and then optionally further doped with additionalmetal-containing components (e.g. metal salt precursors) by impregnationand/or incipient wetness techniques to form bulk catalyst precursors,with such techniques being generally known to those of skill in the art.The bulk catalyst precursors are treated by calcining and/or reducing toform active bulk catalytic materials at discrete regions on the wafersubstrate.

The catalytic materials (e.g., supported or bulk) on the substrate aretested for activity and selectivity for the WGS reaction using ascanning mass spectrometer (“SMS”) comprising a scanning/sniffing probeand a mass spectrometer. More details on the scanning mass spectrometerinstrument and screening procedure are set forth in U.S. Pat. No.6,248,540in European Patent No. EP 101994 and in European PatentApplication No. EP 1186892 and corresponding U.S. Pat. No. 6,864,091filed Aug. 31, 2000 by Wang et al., the complete disclosure of each ofwhich is incorporated herein in its entirety. Generally, the reactionconditions (e.g. contact time and/or space velocities, temperature,pressure, etc.) associated with the scanning mass spectrometer catalystscreening reactor are controlled such that partial conversions (i.e.,non-equilibrium conversions, e.g., ranging from about 10% to about 40%conversion) are obtained in the scanning mass spectrometer, fordiscrimination and ranking of catalyst activities for the variouscatalytic materials being screened. Additionally, the reactionconditions and catalyst loadings are established such that the resultsscale appropriately with the reaction conditions and catalyst loadingsof larger scale laboratory research reactors for WGS reactions. Alimited set of tie-point experiments are performed to demonstrate thescalability of results determined using the scanning mass spectrometerto those using larger scale laboratory research reactors for WGSreactions. See, for example, Example 12 of U.S. Patent Application Ser.No. 60/434,708 entitled “Platinum-Ruthenium Containing CatalystFormulations for Hydrogen Generation,” filed by Hagemeyer et al. on Dec.20, 2002.

Preparative and Testing Procedures

The catalysts and compositions of the present invention were identifiedusing high-throughput experimental technology, with the catalysts beingprepared and tested in library format, as described generally above, andin more detail below. Specifically, such techniques were used foridentifying catalyst compositions that were active and selective as WGScatalysts. As used in these examples, a “catalyst library” refers to anassociated collection of candidate WGS catalysts arrayed on a wafersubstrate, and having at least two, and typically three or more commonmetal components (including metals in the fully reduced state, or in apartially or fully oxidized state, such as metal salts), but differingfrom each other with respect to relative stoichiometry of the commonmetal components.

Depending on the library design and the scope of the investigation withrespect to a particular library, multiple (i.e., two or more) librarieswere typically formed on each wafer substrate. A first group of testwafers each comprised about 100 different catalyst compositions formedon a three-inch wafer substrate, typically with most catalysts beingformed using at least three different metals. A second group of testwafers each comprised about 225 different catalyst compositions on afour-inch wafer substrate, again typically with most catalysts beingformed using at least three different metals. Each test wafer itselftypically comprised multiple libraries. Each library typically comprisedbinary, ternary or higher-order compositions—that is, for example, asternary compositions that comprised at least three components (e.g., A,B, C) combined in various relative ratios to form catalytic materialshaving a molar stoichiometry covering a range of interest (e.g.,typically ranging from about 20% to about 80% or more (e.g to about 100%in some cases) of each component). For supported catalysts, in additionto varying component stoichiometry for the ternary compositions,relative total metal loadings were also investigated.

Typical libraries formed on the first group of (three-inch) test wafersincluded, for example, “five-point libraries” (e.g., twenty libraries,each having five different associated catalyst compositions), or“ten-point” libraries (e.g., ten libraries, each having ten differentassociated catalyst compositions), or “fifteen-point libraries” (e.g.,six libraries, each having fifteen different associated catalystcompositions) or “twenty-point libraries” (e.g., five libraries, eachhaving twenty different associated catalyst compositions). Typicallibraries formed on the second group of (four-inch) test wafersincluded, for example, “nine-point libraries” (e.g., twenty-fivelibraries, each having nine different associated catalyst compositions),or “twenty-five point” libraries (e.g., nine libraries, each havingtwenty-five different associated catalyst compositions). Largercompositional investigations, including “fifty-point libraries” (e.g.,two or more libraries on a test wafer, each having fifty associatedcatalyst compositions), were also investigated. Typically, thestoichiometric increments of candidate catalyst library members rangedfrom about 1.5% (e.g. for a “fifty-five point ternary”) to about 15%(e.g., for a “five-point” ternary). See, generally, for example, WO00/17413 for a more detailed discussion of library design and arrayorganization. FIGS. 9A to 9F of the instant application show librarydesigns for libraries prepared on a common test wafer, as graphicallyrepresented using Library Studio® (Symyx Technologies, Inc., SantaClara, Calif.), where the libraries vary with respect to bothstoichiometry and catalyst loading. Libraries of catalytic materialsthat vary with respect to relative stoichiometry and/or relativecatalyst loading can also be represented in a compositional table, suchas is shown in the several examples of this application.

Referring to FIG. 9A, for example, the test wafer includes ninelibraries, where each of the nine libraries comprise nine differentternary compositions of the same three-component system. In thenomenclature of the following examples, such a test wafer is said toinclude nine, nine-point-ternary (“9PT”) libraries. The library depictedin the upper right hand corner of this test wafer includes catalystcompositions comprising components A, B and X₁ in 9 differentstoichiometries. As another example, with reference to FIG. 9B, apartial test wafer is depicted that includes a fifteen-point-ternary(“15PT”) library having catalyst compositions of Pt, Pd and Cu infifteen various stoichiometries. Generally, the composition of eachcatalyst included within a library is graphically represented by anassociation between the relative amount (e.g., moles or weight) ofindividual components of the composition and the relative area shown ascorresponding to that component. Hence, referring again to the fifteendifferent catalyst compositions depicted on the partial test waferrepresented in FIG. 9B, it can be seen that each composition includes Pt(red), Pd (green) and Cu (blue), with the relative amount of Ptincreasing from column 1 to column 5 (but being the same as comparedbetween rows within a given column), with the relative amount of Pddecreasing from row 1 to row 5 (but being the same as compared betweencolumns within a given row), and with the relative amount of Cudecreasing from a maximum value at row 5 column 1 to a minimum at, forexample, row 1 column 1. FIG. 9C shows a test wafer that includes afifty-point-ternary (“50PT”) library having catalyst compositions of Pt,Pd and Cu in fifty various stoichiometries. This test library could alsoinclude another fifty-point ternary library (not shown), for examplewith three different components of interest.

FIGS. 9D through 9F are graphical representations of two fifty-pointternary libraries (“bis 50PT libraries”) at various stages ofpreparation—including a Pt—Au—Ag/CeO₂ library (shown as the upper rightternary library of FIG. 9E) and a Pt—Au—Ce/ZrO₂ library (shown as thelower left ternary library of FIG. 9E). Note that the Pt—Au—Ag/CeO₂library also includes binary-impregnated compositions—Pt—Au/CeO₂ binarycatalysts (row 2) and Pt—Ag/CeO₂ (column 10). Likewise, thePt—Au—Ce/ZrO₂ library includes binary-impregnatedcompositions—Pt—Ce/ZrO₂ (row 11) and Au—Ce/ZrO₂ (column 1). Briefly, thebis 50PT libraries were prepared by depositing CeO₂ and ZrO₂ supportsonto respective portions of the test wafer as represented graphically inFIG. 9D. The supports were deposited onto the test wafer as a slurry ina liquid media using a liquid handling robot, and the test wafer wassubsequently dried to form dried supports. Thereafter, salts of Pt, Auand Ag were impregnated onto the regions of the test wafer containingthe CeO₂ supports in the various relative stoichiometries as representedin FIG. 9E (upper-right-hand library). Likewise, salts of Pt, Au and Cewere impregnated onto the regions of the test wafer containing the ZrO₂supports in the various relative stoichiometries as represented in FIG.9E (lower-left-hand library). FIG. 9F is a graphical representation ofthe composite library design, including the relative amount of catalystsupport.

Specific compositions of tested catalytic materials of the invention aredetailed in the following examples for selected libraries.

Performance benchmarks and reference experiments (e.g., blanks) werealso provided on each quartz catalyst test wafer as a basis forcomparing the catalyst compositions of the libraries on the test wafer.The benchmark catalytic material formulations included a Pt/zirconiacatalyst standard with about 3% Pt catalyst loading (by weight, relativeto total weight of catalyst and support). The Pt/zirconia standard wastypically synthesized by impregnating 3 μL of, for example, 1.0% or 2.5%by weight Pt stock solution onto zirconia supports on the wafer prior tocalcination and reduction pretreatment.

Typically wafers were calcined in air at a temperature ranging from 300°C. to 500° C. and/or reduced under a continuous flow of 5% hydrogen at atemperature ranging from about 200° C. to about 500° C. (e.g., 450° C.).Specific treatment protocols are described below with respect to each ofthe libraries of the examples.

For testing using the scanning mass spectrometer, the catalyst waferswere mounted on a wafer holder which provided movement in an XY plane.The sniffing/scanning probe of the scanning mass spectrometer moved inthe Z direction (a direction normal to the XY plane of movement for thewafer holder), and approached in close proximity to the wafer tosurround each independent catalyst element, deliver the feed gas andtransmit the product gas stream from the catalyst surface to thequadrupole mass spectrometer. Each element was heated locally from thebackside using a CO₂ laser, allowing for an accessible temperature rangeof about 200° C. to about 600° C. The mass spectrometer monitored sevenmasses for hydrogen, methane, water, carbon monoxide, argon, carbondioxide and krypton: 2, 16, 18, 28, 40, 44 and 84respectively.

Catalyst compositions were tested at various reaction temperatures,typically including for example at about 300° C., 350° C. and/or 400° C.and, additionally, usually for more active formulations, at 250° C.Particularly for LTS formulations, testing of catalytic activity atreaction temperatures starting as low as 200° C. may occur. The feed gastypically consisted of 51.6% H₂, 7.4% Kr, 7.4% CO, 7.4% CO₂ and 26.2%H₂O. The H₂, CO, CO₂ and Kr internal standards are premixed in a singlegas cylinder and then combined with the water feed. Treated water (18.1mega-ohms-cm at 27.5° C.) produced by a Bamnstead Nano Pure Ultra Watersystem was used, without degassing.

Data Processing and Analysis

Data analysis was based on mass balance plots where CO conversion wasplotted versus CO₂ production. The mass spectrometer signals wereuncalibrated for CO and CO₂ but were based on Kr-normalized massspectrometer signals. The software package Spotfire™ (sold by Spotfire,Inc. of Somerville, Mass.) was used for data visualization.

A representative plot of CO conversion versus CO₂ production for a WGSreaction is shown in FIG. 10A involving, for discussion purposes, twoternary catalyst systems—a Pt—Au—Ag/CeO₂ catalyst library and aPt—Au—Ce/ZrO₂ catalyst library—as described above in connection withFIGS. 9D through 9F. The catalyst compositions of these libraries werescreened at four temperatures: 250° C., 300° C., 350° C. and 400° C.With reference to the schematic diagram shown in FIG. 10B, active andhighly selective WGS catalysts (e.g., Line I of FIG. 10B) will approacha line defined by the mass balance for the water-gas-shift reaction (the“WGS diagonal”) with minimal deviation, even at relatively highconversions (i.e., at CO conversions approaching the thermodynamicequilibrium conversion (point “TE” on FIG. 10B)). Highly activecatalysts may begin to deviate from the WGS diagonal due to cross-overto the competing methanation reaction (point “M” on FIG. 10C). Catalystcompositions that exhibit such deviation may still, however, be usefulWGS catalysts depending on the conversion level at which such deviationoccurs. For example, catalysts that first deviate from the WGS diagonalat higher conversion levels (e.g., Line II of FIG. 10B) can be employedas effective WGS catalysts by reducing the overall conversion (e.g., bylowering catalyst loading or by increasing space velocity) to theoperational point near the WGS diagonal. In contrast, catalysts thatdeviate from the WGS diagonal at low conversion levels (e.g., Line IIIof FIG. 10B) will be relatively less effective as WGS catalysts, sincethey are unselective for the WGS reaction even at low conversions.Temperature affects the thermodynamic maximum CO conversion, and canaffect the point of deviation from the mass-balance WGS diagonal as wellas the overall shape of the deviating trajectory, since lowertemperatures will generally reduce catalytic activity. For somecompositions, lower temperatures will result in a more selectivecatalyst, demonstrated by a WGS trajectory that more closelyapproximates the WGS mass-balance diagonal. (See FIG. 10C). Referringagain to FIG. 10A, it can be seen that the Pt—Au—Ag/CeO₂ and thePt—Au—Ce/ZrO₂ catalyst compositions are active and selective WGScatalysts at each of the screened temperatures, and particularly atlower temperatures.

Generally, the compositions on a given wafer substrate were testedtogether in a common experimental run using the scanning massspectrometer and the results were considered together. In thisapplication, candidate catalyst compositions of a particular library onthe substrate (e.g., ternary or higher-order catalysts comprising threeor more metal components) were considered as promising candidates for anactive and selective commercial catalyst for the WGS reaction based on acomparison to the Pt/ZrO₂ standard composition included on that wafer.Specifically, libraries of catalytic materials were deemed to beparticularly preferred WGS catalysts if the results demonstrated that ameaningful number of catalyst compositions in that library comparedfavorably to the Pt/ZrO₂ standard composition included on the wafersubstrate with respect to catalytic performance. In this context, ameaningful number of compositions was generally considered to be atleast three of the tested compositions of a given library. Also in thiscontext, favorable comparison means that the compositions had catalyticperformance that was as good as or better than the standard on thatwafer, considering factors such as conversion, selectivity and catalystloading. All catalyst compositions of a given library were in many casespositively identified as active and selective WGS catalysts even insituations where only some of the library members compared favorably tothe Pt/ZrO₂ standard, and other compositions within that librarycompared less than favorably to the Pt/ZrO₂ standard. In suchsituations, the basis for also including members of the library thatcompared somewhat less favorably to the standard is that these membersin fact positively catalyzed the WGS reaction (i.e. were effective ascatalysts for this reaction). Additionally, it is noted that suchcompositions may be synthesized and/or tested under more optimally tunedconditions (e.g., synthesis conditions, treatment conditions and/ortesting conditions (e.g., temperature)) than occurred during actualtesting in the library format, and significantly, that the optimalconditions for the particular catalytic materials being tested maydiffer from the optimal conditions for the Pt/ZrO₂ standard—such thatthe actual test conditions may have been closer to the optimalconditions for the standard than for some of the particular members.Therefore, it was specifically contemplated that optimization ofsynthesis, treatment and/or screening conditions, within the generallydefined ranges of the invention as set forth herein, would result ineven more active and selective WGS catalysts than what was demonstratedin the experiments supporting this invention. Hence, in view of theforegoing discussion, the entire range of compositions defined by eachof the claimed compositions (e.g., each three-component catalyticmaterial, or each four-component catalytic material) was demonstrated asbeing effective for catalyzing the WGS reaction. Further optimization isconsidered, with various specific advantages associated with variousspecific catalyst compositions, depending on the desired or requiredcommercial application of interest. Such optimization can be achieved,for example, using techniques and instruments such as those described inU.S. Pat. No. 6,149,882 or those described in WO 01/66245 and itscorresponding U.S. applications, U.S. Ser. No. 09/801,390entitled“Parallel Flow Process Optimization Reactor” filed Mar. 7, 2001 by Berghet al., and U.S. Ser. No. 09/801,389, entitled “Parallel Flow ReactorHaving Variable Feed Composition” filed Mar. 7, 2001 by Bergh et al.,each of which are incorporated herein by reference for all purposes.

Additionally, based on the results of screening of initial libraries,selective additional “focus” libraries were selectively prepared andtested to confirm the results of the initial library screening, and tofurther identify better performing compositions, in some cases under thesame and/or different conditions. The test wafers for the focuslibraries typically comprised about 225 different candidate catalystcompositions formed on a four-inch wafer substrate, with one or morelibraries (e.g. associated ternary compositions A, B, C) formed on eachtest wafer. Again, the metal-containing components of a given librarywere typically combined in various relative ratios to form catalystshaving stoichiometry ranging from about 0% to about 100% of eachcomponent, and for example, having stoichiometric increments of about10% or less, typically about 2% or less (e.g., for a “fifty-six pointternary”). Focus libraries are more generally discussed, for example, inWO 00/17413. Such focus libraries were evaluated according to theprotocols described above for the initial libraries.

The raw residual gas analyzer (rga) signal values generated by the massspectrometer for the individual gases are uncalibrated and thereforedifferent gases may not be directly compared. Methane data (mass 16) wasalso collected as a control. The signals are typically standardized byusing the raw rga signal for krypton (mass 84) to remove the effect ofgas flow rate variations. Thus, for each library element, thestandardized signal is determined as, for example, sH₂O=raw H₂O/raw Kr;sCO=raw CO/raw Kr; sCO₂=raw CO₂/raw Kr and so forth.

Blank or inlet concentrations are determined from the average of thestandardized signals for all blank library elements (i.e. libraryelements for which the composition contains at most only support). Forexample, b_(avg) H₂O=average sH₂O for all blank elements in the library;b_(avg) CO=average sCO for all blank elements in the library; and soforth.

Conversion percentages are calculated using the blank averages toestimate the input level (e.g., b_(avg) CO) and the standardized signal(e.g., sCO) as the output for each library element of interest. Thus,for each library element, CO_(conversion)=100×(b_(avg) CO−sCO)/b_(avg)CO and H₂O_(conversion)=100×(b_(avg) H₂O−sH₂O)/b_(avg) H₂O.

The carbon monoxide (CO) to carbon dioxide (CO₂) selectivity isestimated by dividing the amount of CO₂ produced (sCO₂−b_(avg) CO₂) bythe amount of CO consumed (b_(avg) CO−sCO). The CO₂ and CO signals arenot directly comparable because the rga signals are uncalibrated.However, an empirical conversion constant (0.6 CO₂ units=1 CO unit) hasbeen derived, based on the behavior of highly selective standardcatalyst compositions. The selectivity of the highly selective standardcatalyst compositions approach 100% selectivity at low conversion rates.Therefore, for each library element, estimated CO to CO₂selectivity=100×0.6×(sCO₂−b_(avg) CO₂)/(b_(avg) CO−sCO). Low COconsumption rates can produce highly variable results, and thus thereproducibility of CO₂ selectivity is maintained by artificiallylimiting the CO₂ selectivity to a range of 0% to 140%.

The complete disclosure of the above mentioned application and all otherreferences cited herein are incorporated herein in their entireties forall purposes.

The following examples are representative of the screening of librariesthat lead to identification of the particularly claimed inventionsherein.

Example 1

A 4″ quartz wafer was pre-coated with 14 columns of Engelhard Co-164(bulk Co commercial catalyst) and ZrO₂ (Norton XZ16052) as referencecarrier by slurry dispensing as a master batch in volumes of 3 μL (both1.5 g/4 mL, EG/H₂O/MeO 32.5:30:37.5) to a 15×15 square on the wafer.After the dispensing step the wafer was oven-dried at 70° C. for 14minutes.

Six internal standards were synthesized by Cavro spotting 3 μL ofPt(NH₃)₂(NO₂)₂ (stabilized, 2.5% Pt) stock solution into thecorresponding first row/last column positions. The Co-bulk carrierpre-coated wafer was impregnated with a ruthenium(III) nitrosyl nitrate(diluted in dilute nitric acid and containing 1.5% Ru) gradient from topto bottom by Cavro dispensing from the respective stock solution vial toa microtiter plate and diluting with distilled water followed by aone-to-one transfer of the microtiter plate pattern to the wafer. The Rusolution was dispensed in 2.5 μL dispense volume per well resulting in a14×15 point rectangle on the wafer (14 replicas of the 15 point Rugradients).

Subsequently the ZrO₂ pre-coated carrier column no. 15 was impregnatedwith a 15 point single column Pt(NH₃)₂(NO₂)₂ (unstabilized, 1% Pt)gradient from bottom to top by Cavro dispensing from the correspondingstock Pt solution vial to a microtiter plate and diluting with distilledwater followed by a one-to-one transfer to the wafer by dispensing 2.5μL dispense volume per well.

The wafer was slowly dried overnight at room temperature. The Co-bulkcarrier coated columns nos. 2-14 were coated with binary metal-gradientsfrom bottom to top: C2: LiOH, C3: KOH, C4: NaOH, C5: RbOH (C2-C5: 1molar), C6: Fe(NO₃)₃, C7: H₂MoO₄, C8: Ce(III)(NO₃)₃, C9: La(NO₃)₃(C6-C9: 0.25 molar), ClO: H₂IrCl₆ (1% Ir), C11: Cu(NO₃)₂ (0.1 molar),C12: Mn(NO₃)₂ (0.25 molar), C13: Pd(NH₃)₂(NO₂)₂ (1% Pd), C14:Pt(NH₃)₂(NO₂)₂ (unstabilized, 1% Pt), by Cavro dispensing 2.5 μL perwell from the respective stock solution vials as above resulting in a13×15 point rectangle on the wafer. The wafer was slowly dried at roomtemperature for 3 hours and then reduced in a flow of 5%H₂/N₂ at 450° C.for 2 hours. Commercial catalyst was slurried into five positions of thefirst row and last column as external standard (3 μL catalyst slurry).See FIGS. 1A through 1C. The wafer was screened by SMS for WGS activitywith a H₂/CO/CO₂/H₂O mixed feed at 200° C., 230° C. and 260° C.

This set of experiments demonstrated active and selective bulk cobaltsupported WGS catalyst formulations.

Example 2

A 4″ quartz wafer was precoated with ZrO₂ carrier by repeated slurrydispensing of zirconia powder (Norton XZ16052/MEI FZO923/01 70:30 mix)onto the wafer (Ig zirconia powder in 4 mL EG/H₂O 50:50 mixture, 2zirconia layers=2×3 μL=6 μL slurry dispensed in total). The zirconiacarrier-precoated wafer was dried and then impregnated with gradients ofthe metals (Co, Ni, Cu, Fe and Ru). Advantageously, all metal precursorsolutions (metal nitrates and Ru nitrosyl nitrate) are compatible and asingle impregnation step suffices to deposit all the metals. Thegradients were premixed in a microtiter plate by dilution of metalnitrate stock solutions with water. The diluted solutions are thentransferred from the microtiter plate to the wafer by Cavro dispensing(3 μL dispense volume per well). The wafer was dried, calcined in air at500° C. for 1 hour and then reduced in 5% H₂/Ar at 380° C. for 3 hours.See FIGS. 2A and 2B.

The reduced wafer was then screened by SMS for WGS activity with aH₂/CO/CO₂/H₂O mixed feed at 250° C., 300° C., 350° C. and 400° C.

This set of experiments demonstrated active and selective WGS catalystformulations for Ru and Co containing formulations supported onzirconia.

Example 3

A 4″ quartz wafer was precoated with zirconia carrier by repeated slurrydispensing zirconia powder (Norton XZ16052) onto the wafer. The slurrywas composed of 1.5 g zirconia powder in 4 mL of a MEO/EG/H₂O 40:30:30mixture. A total of 3 μL of slurry was deposited on each spot.

The zirconia carrier precoated wafer was impregnated with separateconcentration gradients of Co, Fe, Sm, Ge, Sn and Ti by Cavro dispensingfrom metal stock solution vials to a microtiter plate (five, four, one,two, one, two columns, respectively of each metal in 7-point (“7P”) and8-point (“8P”) concentration gradients) followed by transferringreplicas of the four 7P and 8P columns onto the wafer (2.5 μL dispensevolume per well). The wafer was dried at 70° C. for 10 minutes.

The wafer was then impregnated with Fe, Zr, Ti, Mo, Eu, Sn, Sb and Vconcentration gradients by Cavro dispensing 2.5 μL per well in 7-pointand 8-point gradients. The metal columns were arranged in the followingorder beginning on the left: Fe, Zr, Ti, Mo, Eu, Zr, Ti, Mo, Eu, Eu, Sn,Sb, Sb, V and Mo. For all of the above impregnations, Co, Fe, Sm and Euwere provided as their nitrates, Ge, Sn and V as their oxalates, Ti asthe ammonium titanyl oxalate, Sb as the ammonium antimony oxalate, Zr aszirconyl nitrate and Mo as molybdic acid. The wafer was dried at 70° C.for 10 minutes.

The top seven rows of the wafer were uniformly coated with 2.5 μL perwell of a RuNO(NO₃)₃ stock solution (0.5% Ru), and the bottom eight rowswere uniformly coated with 2.5 μL per well of a Pt(NH₃)₂(NO₂)₂ stocksolution (1% Pt). The wafer was calcined in air at 400° C. for 2 hoursfollowed by reduction with 5% H₂/N₂ at 300° C. for 2 hours. Nineinternal standards were synthesized by spotting 2.5 μL Pt(NH₃)₂(NO₂)₂solution (2.5% Pt) into the corresponding first row/last columnpositions. See FIGS. 3A through 3G.

The reduced library was then screened in SMS for WGS activity with aH₂/CO/CO₂/H₂O mixed feed at 300° C. and 350° C. The CO conversion versusCO₂ production results at 300° C. and 350° C. are presented in FIGS. 3Hand 3I. More detailed test results, such as, CO conversion, CO₂production and CH₄ production at 300° C. and 350° C. for each of the 225individual catalyst wells on the test wafer are presented in Table 1.

This set of experiments demonstrated active and selective WGS catalystformulations of various Ru—Co—{Fe, Zr, Ti, Mo, Eu,}/ZrO₂ formulations onthe wafer.

Example 4

A 3″ quartz wafer was coated with niobia, ceria and magnesia carriers byslurry-dispensing aqueous carrier slurries onto the wafer (4 μLslurry/well, 1 g of carrier powder slurried in 2 mL H₂O for niobia andceria; 500 mg of carrier powder slurried in 2 mL H₂O for magnesia).Niobia carriers were produced by Norton, product numbers 2001250214,2000250356, 2000250355, 2000250354 and 2000250351. Cerias came fromNorton (product numbers 2001080053, 2001080052 and 2001080051) andAldrich (product number 21,157-50. Magnesia was obtained from Aldrich(product number 24,338-8).

The carrier precoated wafer was then loaded with the same Pt gradientfor each carrier in a single impregnation step by liquid dispensing 3 μLPt(NH₃)₂(NO₂)₂ solution (5% Pt) from microtiter plate to wafer. Thewafer was dried and then reduced in 5% H₂/Ar at 450° C. for 2 hours. SeeFIGS. 4A through 4C.

The reduced library was then screened in SMS for WGS activity with aH₂/CO/CO₂/H₂O mixed feed at 250° C., 300° C., 350° C., and 400° C.Results at 250° C., 300° C., 350° C., and 400° C. are presented in FIGS.4D through 4H.

This set of experiments demonstrated active and selective WGS catalystformulations of various Pt on one of Nb oxide, Ce oxide or Mg oxideformulations on the wafer. Various Norton niobia carriers were found tobe very active and selective over a broad temperature range. Nortonceria 2001080051 was found to be very selective at higher temperatures.Magnesia was less active than either of niobia or ceria but did exhibithighly selective WGS performance.

Example 5

A 4″ quartz wafer was coated with fourteen different catalyst carriersby slurry-dispensing the carrier slurries onto the wafer. Each wafercolumn was coated with a different carrier, except for columns 14 and 15which were both coated with gamma-alumina, described below:

Ceria, 99.5% purity; 9 to 15 nm particle size; BET (m²/g): 55-95; Alfa43136; dispensed onto the wafer from a slurry of 0.75 g powder slurriedin 4 mL ethylene glycol (“EG”)/H₂O/MEO 40:30:30 mixture.

Ceria, produced by the low temperature calcination of precipitated Cehydroxide; dispensed onto the wafer from a slurry of 1.5 g powderslurried in 4 mL EG/H₂O/MEO 40:30:30 mixture.

Zirconia; 99.8% purity; BET (m²/g): greater than 90; Norton XZ16052;dispensed onto the wafer from a slurry of 1.5 g powder slurried in 4 mLEG/H₂O/MEO 40:30:30 mixture.

Zirconia; 99.8% purity; BET (m²/g): 269; Norton XZ16154; dispensed ontothe wafer from a slurry of 1.5 g powder slurried in 4 mL EG/H₂O/MEO40:30:30 mixture.

Titania; BET (m²/g): 45; Degussa Aerolyst 7708; dispensed onto the waferfrom a slurry of 1.0 g powder slurried in 4 mL EG/H₂O/MEO 40:30:30mixture.

Titania; 99% purity; BET (m²/g): 37; Norton XT25384; dispensed onto thewafer from a slurry of 1.0 g powder slurried in 4 mL EG/H₂O/MEO 40:30:30mixture.

Niobia; 97% purity; BET (m²/g): 27; Norton 2000250355; dispensed ontothe wafer from a slurry of 1.0 g powder slurried in 4 mL EG/H₂O/MEO40:30:30 mixture.

Lanthania; 99.999% purity; Gemre-5N from Gemch Co., Ltd. (Shanghai,China); dispensed onto the wafer from a slurry of 1.5 g powder slurriedin 4 mL EG/H₂O/MEO 40:30:30 mixture.

Mixed Fe—Ce—O; coprecipitated Fe and Ce oxalate; calcined at 360° C.;dispensed onto the wafer from a slurry of 1.0 g powder slurried in 4 mLEG/H₂O/MEO 40:30:30 mixture.

Mixed La—Ce—O; coprecipitated La and Ce oxalate; calcined at 760° C.;dispensed onto the wafer from a slurry of 1.0 g powder slurried in 4 mLEG/H₂O/MEO 40:30:30 mixture.

Mixed Sb₃O₄—SnO₂ carrier from Alfa; 99.5% purity; BET (m²/g): 30-80;Sb₃O₄:SnO₂ ratio is 10:90 by weight; dispensed onto the wafer from aslurry of 1.0 g powder slurried in 4 mL EG/H₂O/MEO 40:30:30 mixture.

Mixed Fe—Cr—Al—O; commercially available high temperature water gasshift catalyst; dispensed onto the wafer from a slurry of 1.0 g powderslurried in 4 mL EG/H₂O/MEO 40:30:30 mixture.

Fe₂O₃/FeOOH; BET (m²/g): 14; 50:50 physical mixture of commercialpowders (Bayferrox 720N: Bayoxide E3920 from Bayer); dispensed onto thewafer from a slurry of 1.0 g powder slurried in 4 mL EG/H₂O/MEO 40:30:30mixture.

14 and 15) Gamma-Al₂O₃; BET (m²/g): 150; Condea Catalox Sbal 50;dispensed onto the wafer from a slurry of 1.0 g powder slurried in 4 mLEG/H₂O/MEO 40:30:30 mixture.

In all cases, except for carrier 1the slurries were applied in 3μl/well; carrier 1 was deposited as two aliquots of 3 μL per well. Thewafer was then dried at 70° C. for 10 minutes.

Columns 14 and 15 were coated with 2.5 μl/well of zirconyl nitrate(0.25M) and lanthanum nitrate (0.25M), respectively, then dried for 10minutes at 70° C. The first 13 columns of the carrier coated wafer werethen loaded with a 15 point Pt gradient by liquid dispensing of 3 μLPt(NH₃)₂(NO₂)₂ solution (1% Pt) from microtiter plate to wafer. Thewafer was dried at 70° C. for 10 minutes. Columns 14 and 15 were thenloaded with a 15 point Pt gradient by liquid dispensing of 3 μLPt(NH₃)₂(NO₂)₂ solution (1% Pt) from microtiter plate to wafer. Thewafer was dried at 70° C. for 10 minutes, calcined in air at 350° C. for2 hours, then reduced in 5% H₂/Ar at 450° C. for 2 hours. Six internalstandards were synthesized by spotting 3 μL Pt(NH₃)₂(NO₂)₂ solution(1.0% Pt) into the corresponding first row/last column positions. SeeFIGS. 5A through 5F.

The reduced library was then screened in SMS for WGS activity with aH₂/CO/CO₂/H₂O mixed feed at 250° C. and 300° C. The CO conversion versusCO₂ production results at 250 ° C. and 300° C. are presented in FIGS.5G, 5H and 5I. More detailed test results, such as, CO conversion, CO₂production and CH₄ production at 250° C. and 300° C. for each of the 225individual catalyst wells on the test wafer are presented in Table 2.

This set of experiments demonstrated active and selective WGS catalystformulations of various Pt on various of the oxide carrier formulationson the wafer.

Example 6

Scale-up catalyst samples were prepared by using incipient wetnessimpregnation of 0.75 grams of ZrO₂ support (Norton, 80-120 mesh) whichhad been weighed into a 10-dram vial. Aqueous metal precursor saltsolutions were then added in the order: Ru, Fe, one of Co or Mo, thenNa. The precursor salt solutions were ruthenium (III) nitrosylnitrate(1.5% Ru (w/v)), iron (III) nitrate (1.0M), cobalt (II) nitrate (1.0M),molybdic acid (1.0M), and sodium hydroxide (3.0N). All starting reagentswere nominally research grade and purchased from Aldrich, Strem, orAlfa. Following each metal addition, the catalysts were dried at 80° C.overnight and then calcined in air as follows:

-   -   After Ru addition—450° C. for 3 hours    -   After Fe addition—450° C. for 3 hours    -   After Co or Mo addition—450° C. for 3 hours for Co, 350° C. for        3 hours for Mo.    -   Following Na addition, the catalysts were calcined at 300° C.        for 3 hours, and then the catalysts were reduced in-situ at        300° C. for 3 hours in a 10% H₂/N₂ feed.        Catalyst Testing Conditions

Catalysts were tested in a fixed bed reactor. Approximately 0.15 g ofcatalyst was weighed and mixed with an equivalent mass of SiC. Themixture was loaded into a reactor and heated to reaction temperature.Reaction gases were delivered via mass flow controllers (Brooks) withwater introduced with a metering pump (Quizix). The composition of thereaction mixture was as follows: H₂ 50%, CO 10%, CO₂ 10%, and H₂O 30%.The reactant mixture was passed through a pre-heater before contactingthe catalyst bed. Following reaction, the product gases were analyzedusing a micro gas chromatograph (Varian Instruments, or Shimadzu).Compositional data on the performance diagram (FIG. 6) is on a dry basiswith water removed.

Testing Results

FIG. 6 shows the CO composition in the product stream following thescale-up testing at a gas hour space velocity of 50,000 h⁻¹.

TABLE 3 Catalyst Compositions (mass ratio) Row Col Support Ru Co Fe NaMo A 1 0.95 0.01 0.005 0.01 0.025 0 A 2 0.94 0.01 0.005 0.02 0.025 0 A 30.93 0.01 0.005 0.03 0.025 0 A 4 0.94 0.02 0.005 0.01 0.025 0 A 5 0.930.02 0.005 0.02 0.025 0 A 6 0.92 0.02 0.005 0.03 0.025 0 B 1 0.945 0.010.01 0.01 0.025 0 B 2 0.935 0.01 0.01 0.02 0.025 0 B 3 0.925 0.01 0.010.03 0.025 0 B 4 0.935 0.02 0.01 0.01 0.025 0 B 5 0.925 0.02 0.01 0.020.025 0 B 6 0.915 0.02 0.01 0.03 0.025 0 C 1 0.95 0.01 0 0.01 0.0250.005 C 2 0.94 0.01 0 0.02 0.025 0.005 C 3 0.93 0.01 0 0.03 0.025 0.005C 4 0.94 0.02 0 0.01 0.025 0.005 C 5 0.93 0.02 0 0.02 0.025 0.005 C 60.92 0.02 0 0.03 0.025 0.005 D 1 0.945 0.01 0 0.01 0.025 0.01 D 2 0.9350.01 0 0.02 0.025 0.01 D 3 0.925 0.01 0 0.03 0.025 0.01 D 4 0.935 0.02 00.01 0.025 0.01 D 5 0.925 0.02 0 0.02 0.025 0.01 D 6 0.915 0.02 0 0.030.025 0.01

Example 7

Scale-up catalyst samples were prepared by using incipient wetnessimpregnation of 0.75 grams of ZrO₂ support (Norton, 80-120 mesh) whichhad been weighed into a 10-dram vial. Aqueous metal precursor saltsolutions were then added in the order: Ru, one of Co or Mo, then one ofNa or K. The precursor salt solutions were ruthenium (III)nitrosylnitrate (1.5% Ru w/v)), cobalt (II) nitrate (1.0M), molybdicacid (1.0M), potassium hydroxide (13.92% K w/v)), and sodium hydroxide(3.0N). All starting reagents were nominally research grade andpurchased from Aldrich, Strem, or Alfa. Following each metal addition,the catalysts were dried at 80° C. overnight and then calcined in air asfollows:

-   -   After Ru addition—450° C. for 3 hours    -   After Co or Mo addition—450° C. for 3 hours for Co, 350° C. for        3 hours for Mo    -   After Na or K addition—300° C. for 3 hours    -   Following Na addition, the catalysts were calcined at 300° C.        for 3 hours, and then the catalysts were reduced in-situ at        300° C. for 3 hours in a 10% H₂/N₂ feed.        Catalyst Testing Conditions

Catalysts were tested in a fixed bed reactor. Approximately 0.15 g ofcatalyst was weighed and mixed with an equivalent mass of SiC. Themixture was loaded into a reactor and heated to reaction temperature.Reaction gases were delivered via mass flow controllers (Brooks) withwater introduced with a metering pump (Quizix). The composition of thereaction mixture was as follows: H₂ 50%, CO 10%, CO₂ 10%, and H₂O 30%.The reactant mixture was passed through a pre-heater before contactingthe catalyst bed. Following reaction, the product gases were analyzedusing a micro gas chromatograph (Varian Instruments, or Shimadzu).Compositional data on the performance diagram (FIG. 7) is on a dry basiswith water removed.

Testing Results

FIG. 7 shows the CO composition in the product stream following thescale-up testing at a gas hour space velocity of 50,000 h⁻¹.

TABLE 4 Catalyst Compositions (mass ratio) Row Col Support Ru Co Na K MoA 1 0.95 0.02 0.005 0.025 0 0 A 2 0.925 0.02 0.005 0.05 0 0 A 3 0.930.04 0.005 0.025 0 0 A 4 0.95 0.02 0.005 0 0.025 0 A 5 0.925 0.02 0.0050 0.05 0 A 6 0.93 0.04 0.005 0 0.025 0 B 1 0.945 0.02 0.01 0.025 0 0 B 20.92 0.02 0.01 0.05 0 0 B 3 0.925 0.04 0.01 0.025 0 0 B 4 0.945 0.020.01 0 0.025 0 B 5 0.92 0.02 0.01 0 0.05 0 B 6 0.925 0.04 0.01 0 0.025 0C 1 0.95 0.02 0 0.025 0 0.005 C 2 0.925 0.02 0 0.05 0 0.005 C 3 0.930.04 0 0.025 0 0.005 C 4 0.95 0.02 0 0 0.025 0.005 C 5 0.925 0.02 0 00.05 0.005 C 6 0.93 0.04 0 0 0.025 0.005 D 1 0.945 0.02 0 0.025 0 0.01 D2 0.92 0.02 0 0.05 0 0.01 D 3 0.925 0.04 0 0.025 0 0.01 D 4 0.945 0.02 00 0.025 0.01 D 5 0.92 0.02 0 0 0.05 0.01 D 6 0.925 0.04 0 0 0.025 0.01

Example 8

Scale-up catalyst samples were prepared by using incipient wetnessimpregnation of 0.75 grams of ZrO₂ support (Norton, 80-120 mesh) whichhad been weighed into a 10-dram vial. Aqueous metal precursor saltsolutions were then added in the order: Ru, Fe, Mo and K. The precursorsalt solutions were ruthenium (III) nitrosylnitrate (1.5% Ru (w/v)),iron (III) nitrate (1.0M), molybdic acid (1.0M), and potassium hydroxide(13.92% K (w/v)). All starting reagents were nominally research gradeand purchased from Aldrich, Strem, or Alfa.

Following each metal addition, the catalysts were dried at 80° C.overnight and then calcined in air as follows:

-   -   After Ru addition—450° C. for 3 hours    -   After Fe addition—450° C. for 3 hours    -   After Mo addition—350° C. for 3 hours.    -   Following K addition, the catalysts were calcined at 300° C. for        3 hours, and then the catalysts were reduced in-situ at 300° C.        for 3 hours in a 10% H₂/N₂ feed.        Catalyst Testing Conditions

Catalysts were tested in a fixed bed reactor. Approximately 0.15 g ofcatalyst was weighed and mixed with an equivalent mass of SiC. Themixture was loaded into a reactor and heated to reaction temperature.Reaction gases were delivered via mass flow controllers (Brooks) withwater introduced with a metering pump (Quizix). The composition of thereaction mixture was as follows: H₂ 50%, CO 10%, CO₂ 10%, and H₂O 30%.The reactant mixture was passed through a pre-heater before contactingthe catalyst bed. Following reaction, the product gases were analyzedusing a micro gas chromatograph (Varian Instruments, or Shimadzu).Compositional data on the performance diagram is on a dry basis withwater removed.

Testing Results

FIG. 8 shows the CO composition in the product stream following thescale-up testing at a gas hour space velocity of 50,000 h⁻¹.

TABLE 5 Catalyst Compositions (mass ratio) Row Col Zr Oxide Ru Water FeMo K A 1 90.5 1 0 1.5 2 5 A 2 89 1 0 3 2 5 A 3 89.5 2 0 1.5 2 5 A 4 88 20 3 2 5 A 5 88.5 3 0 1.5 2 5 A 6 87 3 0 3 2 5 B 1 88.5 1 0 1.5 4 5 B 287 1 0 3 4 5 B 3 87.5 2 0 1.5 4 5 B 4 86 2 0 3 4 5 B 5 86.5 3 0 1.5 4 5B 6 85 3 0 3 4 5 C 1 86.5 1 0 1.5 6 5 C 2 85 1 0 3 6 5 C 3 85.5 2 0 1.56 5 C 4 84 2 0 3 6 5 C 5 84.5 3 0 1.5 6 5 C 6 83 3 0 3 6 5 D 1 84.5 1 01.5 8 5 D 2 83 1 0 3 8 5 D 3 83.5 2 0 1.5 8 5 D 4 82 2 0 3 8 5 D 5 82.53 0 1.5 8 5 D 6 81 3 0 3 8 5

Example 9

Scale-up catalyst samples were prepared by using incipient wetnessimpregnation of 0.75 grams of ZrO₂ support (Norton, 80-120 mesh) whichhad been weighed into a 10-dram vial. Aqueous metal precursor saltsolutions were then added in the order: Ru, Fe, Co, K. The precursorsalt solutions were ruthenium (III) nitrosylnitrate (1.5% Ru (w/v)),iron (III) nitrate (1.0M), cobalt (II) nitrate (1.0M), and potassiumhydroxide (13.92% K (w/v)). All starting reagents were nominallyresearch grade purchased from Aldrich, Strem, or Alfa. Following eachmetal addition, the catalysts were dried at 80° C. overnight and thencalcined in air as follows:

-   -   After Ru addition—450° C. for 3 hours    -   After Fe or Co addition—450° C. for 3 hours    -   Following K addition, the catalysts were calcined at 300° C. for        3 hours, and then the catalysts were reduced in-situ at 300° C.        for 3 hours in a 10% H₂/N₂ feed.        Catalyst Testing Conditions

Catalysts were tested in a fixed bed reactor. Approximately 0.15 g ofcatalyst was weighed and mixed with an equivalent mass of SiC. Themixture was loaded into a reactor and heated to reaction temperature.Reaction gases were delivered via mass flow controllers (Brooks) withwater introduced with a metering pump (Quizix). The composition of thereaction mixture was as follows: H₂ 50%, CO 10%, CO₂ 10%, and H₂O 30%.The reactant mixture was passed through a pre-heater before contactingthe catalyst bed. Following reaction, the product gases were analyzedusing a micro gas chromatograph (Varian Instruments, or Shimadzu).Compositional data on the performance diagrams (FIGS. 11A-11D) is on adry basis with water removed.

Testing Results

FIGS. 11A-11D show the CO composition in the product stream followingthe scale-up testing at a gas hour space velocity of 50,000 h⁻¹.

TABLE 6 Catalyst Compositions (mass ratio) Row Col ZrO2 Ru Water Co Fe KA 1 90.5 1 0 2 1.5 5 A 2 89 1 0 2 3 5 A 3 89.5 2 0 2 1.5 5 A 4 88 2 0 23 5 A 5 88.5 3 0 2 1.5 5 A 6 87 3 0 2 3 5 B 1 88.5 1 0 4 1.5 5 B 2 87 10 4 3 5 B 3 87.5 2 0 4 1.5 5 B 4 86 2 0 4 3 5 B 5 86.5 3 0 4 1.5 5 B 685 3 0 4 3 5 C 1 86.5 1 0 6 1.5 5 C 2 85 1 0 6 3 5 C 3 85.5 2 0 6 1.5 5C 4 84 2 0 6 3 5 C 5 84.5 3 0 6 1.5 5 C 6 83 3 0 6 3 5 D 1 84.5 1 0 81.5 5 D 2 83 1 0 8 3 5 D 3 83.5 2 0 8 1.5 5 D 4 82 2 0 8 3 5 D 5 82.5 30 8 1.5 5 D 6 81 3 0 8 3 5

TABLE I Pt 1.0%/ R C COCONV H2OCONV CO2PROD CO2PERPROD CH4PROD ZrO2_stdCoNO32 EuNO33 FeNO33 GeOX2 real real real real real real real real realreal real real Temperature: 300 C. 1 1 23.3979 17.6501 0.8779 32.16860.1664 0.1275 0 0 0 0 1 2 −1.1124 2.3706 0.0639 2.3411 −0.0021 0 0 0 0 01 3 −1.6949 −0.2659 0.0004 0.0153 −0.0197 0 0 0 0 0 1 4 −0.9915 −0.9487−0.0014 −0.0495 −0.0142 0 0 0 0 0 1 5 −1.0565 −0.9397 −0.0055 −0.20280.006 0 0 0 0 0 1 6 −0.2855 −1.2793 0.0103 0.3777 0.0113 0 0 0 0 0 1 728.1097 14.6816 0.884 32.3895 0.1642 0.1275 0 0 0 0 1 8 0.9205 0.10620.0127 0.4649 0.0073 0 0 0 0 0 1 9 0.0356 −1.2127 −0.0144 −0.526 0.00470 0 0 0 0 1 10 0.4156 −0.3077 −0.0403 −1.4774 −0.0011 0 0 0 0 0 1 11−0.3764 −1.461 −0.0249 −0.9141 0.0025 0 0 0 0 0 1 12 0.4943 −3.1959−0.0361 −1.3215 −0.0022 0 0 0 0 0 1 13 29.6605 16.477 0.889 32.57330.1568 0.1275 0 0 0 0 1 14 0.6281 0.4304 0.0161 0.5889 0.0067 0 0 0 0 01 15 −0.4669 0.4829 −0.0098 −0.3608 −0.0045 0 0 0 0 0 1 16 28.595813.6924 0.8373 30.6782 0.1771 0.1275 0 0 0 0 2 1 30.3699 3.2528 0.601822.0522 0.2851 0 0.25 0 1 0 2 2 48.2195 −19.2657 0.2569 9.4134 0.7193 00.25 0 0 0 2 3 2.2358 1.0554 −0.0058 −0.2137 0.0006 0 0.25 0 0 0 2 41.2688 −0.8847 −0.036 −1.3205 −0.006 0 0.25 0 0 0 2 5 38.8162 −0.95050.5676 20.7966 0.4232 0 0.25 1 0 0 2 6 47.6199 −17.3385 0.2795 10.24230.6874 0 0 0 0.25 0 2 7 3.2285 0.9305 0.0546 1.9987 0.0088 0 0 0 0.25 02 8 0.7573 −1.6324 −0.0351 −1.2856 −0.0045 0 0 0 0.25 0 2 9 50.4749−16.5634 0.3774 13.8299 0.7065 0 0 1 0.25 0 2 10 51.7365 −19.3288 0.318711.6785 0.7727 0 0 1 0 0 2 11 5.2973 2.6408 0.1166 4.2723 0.0127 0 0 0 00.125 2 12 1.3503 −1.7415 0.0672 2.463 0.0176 0 0 0 0 0.125 2 13 0.7721−1.469 0.035 1.2834 0.0106 0 0 0 0 0 2 14 0.8812 1.1019 −0.0379 −1.3879−0.0069 0 0 0 0 0 2 15 0.8316 0.8283 −0.0398 −1.4583 −0.0074 0 0 0 0 0 216 0.5817 1.191 −0.0029 −0.1064 −0.002 0 0 0 0 0 3 1 30.2645 3.96010.5989 21.9446 0.2807 0 0.375 0 0.875 0 3 2 38.6623 −1.5892 0.554520.3157 0.4281 0 0.375 0 0 0 3 3 19.5212 −0.9826 0.2651 9.7142 0.2008 00.375 0 0 0 3 4 1.6135 −0.2621 −0.0409 −1.4989 −0.0092 0 0.375 0 0 0 3 546.3268 −10.8594 0.5019 18.3905 0.6022 0 0.375 0.875 0 0 3 6 44.4463−11.6329 0.3999 14.6543 0.5794 0 0 0 0.375 0 3 7 3.9453 0.1646 0.08263.0254 0.0151 0 0 0 0.375 0 3 8 0.74 0.6287 −0.0325 −1.1919 −0.0042 0 00 0.375 0 3 9 38.6781 −2.952 0.6094 22.3277 0.4362 0 0 0.875 0.375 0 310 54.7072 −25.9679 0.2052 7.5179 0.8253 0 0 0.875 0 0 3 11 5.9726−0.7412 0.1289 4.7248 0.027 0 0 0 0 0.1875 3 12 3.4876 0.0838 0.12184.4615 0.0136 0 0 0 0 0.1875 3 13 1.0476 −1.4924 0.0221 0.8115 0.01 0 00 0 0 3 14 0.3148 −0.6654 −0.0142 −0.5186 −0.0004 0 0 0 0 0 3 15 0.68770.4516 −0.0215 −0.786 −0.0053 0 0 0 0 0 3 16 1.0421 −0.5165 −0.0228−0.8351 −0.0024 0 0 0 0 0 4 1 31.8656 4.81 0.6217 22.7782 0.3062 0 0.5 00.75 0 4 2 46.6604 −11.5493 0.4504 16.5016 0.6186 0 0.5 0 0 0 4 333.8092 −1.1877 0.5484 20.094 0.3832 0 0.5 0 0 0 4 4 1.2781 −1.9499−0.0427 −1.565 −0.0016 0 0.5 0 0 0 4 5 48.8692 −11.6772 0.4364 15.99070.6563 0 0.5 0.75 0 0 4 6 34.8388 0.9453 0.6216 22.7751 0.3756 0 0 0 0.50 4 7 10.5703 7.3969 0.2982 10.9264 0.0465 0 0 0 0.5 0 4 8 1.3085 0.3801−0.0317 −1.1612 −0.0068 0 0 0 0.5 0 4 9 42.2707 −3.7441 0.6055 22.18530.4907 0 0 0.75 0.5 0 4 10 53.9575 −19.4847 0.2258 8.2745 0.8018 0 00.75 0 0 4 11 5.0398 3.7753 0.1549 5.6749 0.0146 0 0 0 0 0.25 4 124.6581 3.909 0.1452 5.3203 0.0187 0 0 0 0 0.25 4 13 1.2289 −0.657 0.05441.9929 0.0024 0 0 0 0 0 4 14 −0.7192 −1.6325 −0.0009 −0.033 −0.0001 0 00 0 0 4 15 0.3784 1.3939 −0.0097 −0.3555 −0.0066 0 0 0 0 0 4 16 30.45919.7211 0.9002 32.9827 0.2051 0.1275 0 0 0 0 5 1 40.6212 −6.0883 0.558420.4618 0.5161 0 0.625 0 0.625 0 5 2 46.6688 −10.8634 0.4511 16.52750.6095 0 0.625 0 0 0 5 3 37.3834 −4.2781 0.6047 22.1564 0.4299 0 0.625 00 0 5 4 1.5669 −1.5995 −0.0017 −0.0608 0.0052 0 0.625 0 0 0 5 5 50.1298−14.1131 0.4211 15.431 0.6857 0 0.625 0.625 0 0 5 6 26.6419 6.05230.6434 23.5728 0.2194 0 0 0 0.625 0 5 7 8.6684 6.7946 0.281 10.29650.044 0 0 0 0.625 0 5 8 0.9779 −0.036 −0.0176 −0.646 −0.0031 0 0 0 0.6250 5 9 35.2543 4.8589 0.707 25.9058 0.3505 0 0 0.625 0.625 0 5 10 54.6799−21.1561 0.2062 7.555 0.8254 0 0 0.625 0 0 5 11 5.2084 1.4731 0.12434.5549 0.0232 0 0 0 0 0.3125 5 12 5.3536 4.3433 0.119 4.3591 0.0158 0 00 0 0.3125 5 13 3.2025 3.1382 0.0441 1.6145 0.0006 0 0 0 0 0 5 14 0.2153−1.9202 −0.0269 −0.9849 0.0033 0 0 0 0 0 5 15 −0.2673 −0.4322 −0.0057−0.2088 0.0023 0 0 0 0 0 5 16 1.4925 1.2273 −0.0321 −1.1769 −0.0028 0 00 0 0 6 1 42.7555 −9.0717 0.5395 19.7664 0.5614 0 0.75 0 0.5 0 6 245.8288 −8.9258 0.4996 18.3052 0.6147 0 0.75 0 0 0 6 3 41.5856 −1.7080.6264 22.9528 0.4638 0 0.75 0 0 0 6 4 8.6842 3.2728 0.2394 8.77030.0789 0 0.75 0 0 0 6 5 48.6176 −9.6213 0.494 18.1009 0.6381 0 0.75 0.50 0 6 6 19.4889 12.4448 0.6144 22.5119 0.093 0 0 0 0.75 0 6 7 7.72946.7291 0.224 8.2082 0.0237 0 0 0 0.75 0 6 8 1.568 1.0613 −0.0066 −0.2431−0.0058 0 0 0 0.75 0 6 9 29.3086 6.7237 0.7747 28.3872 0.2406 0 0 0.50.75 0 6 10 53.6339 −21.8164 0.2285 8.3731 0.8224 0 0 0.5 0 0 6 114.0289 0.0813 0.1556 5.7026 0.023 0 0 0 0 0.375 6 12 5.1746 4.35240.1794 6.5737 0.0211 0 0 0 0 0.375 6 13 1.4512 2.879 0.0482 1.76730.0029 0 0 0 0 0 6 14 0.4336 −0.8716 −0.0129 −0.4724 −0.0026 0 0 0 0 0 615 0.2211 1.8141 −0.0139 −0.5078 0.0013 0 0 0 0 0 6 16 −0.0657 −3.425−0.0004 −0.0161 0.004 0 0 0 0 0 7 1 41.5803 −4.985 0.5682 20.8201 0.49820 0.875 0 0.375 0 7 2 47.1338 −11.2481 0.5085 18.6316 0.6103 0 0.875 0 00 7 3 45.8276 −6.9809 0.5901 21.6228 0.5654 0 0.875 0 0 0 7 4 21.17510.8262 0.4392 16.0913 0.1988 0 0.875 0 0 0 7 5 50.5559 −10.6652 0.45616.7087 0.6675 0 0.875 0.375 0 0 7 6 18.5797 12.0318 0.5791 21.21790.0952 0 0 0 0.875 0 7 7 7.6851 6.2622 0.2593 9.5003 0.0357 0 0 0 0.8750 7 8 2.1045 3.9298 0.0514 1.8836 0.0033 0 0 0 0.875 0 7 9 23.490813.6669 0.7203 26.3928 0.1327 0 0 0.375 0.875 0 7 10 54.4598 −21.58180.2172 7.9573 0.8271 0 0 0.375 0 0 7 11 3.7186 −1.2656 0.075 2.74670.0105 0 0 0 0 0.4375 7 12 2.827 1.4339 0.0698 2.5567 0.0063 0 0 0 00.4375 7 13 1.9615 1.707 0.0366 1.3395 −0.0002 0 0 0 0 0 7 14 −0.0274−0.1067 0.0019 0.0688 −0.0016 0 0 0 0 0 7 15 0.8994 1.106 0.0047 0.1708−0.0071 0 0 0 0 0 7 16 30.8134 14.3524 0.9204 33.7256 0.1884 0.1275 0 00 0 8 1 46.3783 −12.2162 0.4321 15.8338 0.6164 0 1 0 0.25 0 8 2 44.5641−10.505 0.5104 18.703 0.5958 0 1 0 0 0 8 3 47.4226 −10.0949 0.499918.3152 0.6142 0 1 0 0 0 8 4 37.7282 −2.9706 0.5252 19.2438 0.427 0 1 00 0 8 5 50.5051 −16.1451 0.4166 15.2631 0.7211 0 1 0.25 0 0 8 6 19.632312.9015 0.6158 22.5634 0.0913 0 0 0 1 0 8 7 12.2427 5.4119 0.473217.3376 0.0668 0 0 0 1 0 8 8 4.2221 1.9282 0.1254 4.5931 0.0122 0 0 0 10 8 9 23.6045 9.2959 0.7335 26.8765 0.1392 0 0 0.25 1 0 8 10 54.6039−25.8495 0.233 8.5383 0.849 0 0 0.25 0 0 8 11 0.5013 0.0578 0.04521.6557 0.0072 0 0 0 0 0.5 8 12 1.9219 −1.225 0.0822 3.0101 0.0059 0 0 00 0.5 8 13 1.8321 2.8238 0.037 1.3557 −0.0006 0 0 0 0 0 8 14 0.5852−0.4161 0.0039 0.1447 −0.0008 0 0 0 0 0 8 15 0.9488 1.6851 0.0107 0.3927−0.0024 0 0 0 0 0 8 16 −0.4407 −0.5431 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0.0971 3.557 0.0118 0 0 0 0 0.4464 15 136.9332 5.3004 0.239 8.7581 0.0301 0 0 0 0 0 15 14 26.1972 17.7664 0.924633.8768 0.1274 0 0 0 0 0 15 15 19.1845 13.9445 0.6907 25.308 0.0867 0 00 0 0 15 16 0.3649 1.2108 0.0114 0.417 0.0013 0 0 0 0 0 16 1 31.51048.4474 0.7941 29.0962 0.2773 0 1 0 0.25 0 16 2 30.5115 5.3385 0.639223.4191 0.2956 0 1 0 0 0 16 3 23.9074 9.3043 0.6646 24.3523 0.2003 0 1 00 0 16 4 30.1458 6.5627 0.6574 24.0884 0.2925 0 1 0 0 0 16 5 33.7675.1741 0.6841 25.0644 0.3459 0 1 0.25 0 0 16 6 18.4538 13.526 0.657124.0755 0.0843 0 0 0 1 0 16 7 20.563 14.4049 0.7577 27.7617 0.0961 0 0 01 0 16 8 17.5783 13.2187 0.6339 23.2251 0.0827 0 0 0 1 0 16 9 21.749316.2531 0.8045 29.4783 0.1022 0 0 0.25 1 0 16 10 25.8893 15.2743 0.853831.285 0.1391 0 0 0.25 0 0 16 11 2.7491 2.4376 0.1242 4.5505 0.0171 0 00 0 0.5 16 12 2.0448 2.8285 0.076 2.7833 0.0111 0 0 0 0 0.5 16 13 7.98517.5262 0.2931 10.7401 0.0356 0 0 0 0 0 16 14 22.9038 14.1937 0.742627.2083 0.135 0 0 0 0 0 16 15 14.858 11.7766 0.5425 19.8783 0.0705 0 0 00 0 16 16 29.1421 17.6363 0.9834 36.0309 0.1491 0.1275 0 0 0 0Temperature: 350 C. 1 1 22.4214 6.5014 0.5454 19.7201 0.1953 0.1275 0 00 0 1 2 1.7185 1.5608 0.0349 1.2612 0.0065 0 0 0 0 0 1 3 −0.1941 0.7087−0.0196 −0.7098 −0.0008 0 0 0 0 0 1 4 −1.0642 −2.473 −0.0173 −0.62680.002 0 0 0 0 0 1 5 −0.479 −0.5612 −0.0014 −0.0496 −0.0055 0 0 0 0 0 1 6−0.1345 −0.1753 −0.0024 −0.0857 0.0027 0 0 0 0 0 1 7 26.1459 5.1090.5818 21.0379 0.2509 0.1275 0 0 0 0 1 8 0.5431 0.7417 0.0229 0.82750.0057 0 0 0 0 0 1 9 0.1948 −0.0096 −0.0048 −0.1738 −0.0071 0 0 0 0 0 110 −0.8981 −0.2409 −0.0105 −0.3787 −0.0069 0 0 0 0 0 1 11 −0.4726−0.1975 −0.0234 −0.8455 −0.0009 0 0 0 0 0 1 12 −0.1521 −0.6219 −0.0238−0.8601 −0.0022 0 0 0 0 0 1 13 27.1614 5.4631 0.5987 21.6474 0.25270.1275 0 0 0 0 1 14 0.7324 −0.3447 0.0241 0.8698 0.0057 0 0 0 0 0 1 15−0.0029 −0.0874 −0.0175 −0.6323 −0.001 0 0 0 0 0 1 16 25.7179 2.42590.5272 19.0634 0.2622 0.1275 0 0 0 0 2 1 22.6926 2.7615 0.4684 16.93640.2288 0 0.25 0 1 0 2 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0 0 0 0 0 1515 11.8365 10.8458 0.4323 15.6305 0.0497 0 0 0 0 0 15 16 −0.051 1.73240.0034 0.1232 −0.0097 0 0 0 0 0 16 1 22.6757 6.4052 0.6373 23.04450.1747 0 1 0 0.25 0 16 2 16.9639 5.8 0.4231 15.2985 0.1476 0 1 0 0 0 163 12.2625 5.8522 0.3541 12.803 0.0917 0 1 0 0 0 16 4 18.6795 6.34180.4487 16.2244 0.1661 0 1 0 0 0 16 5 20.9223 5.4399 0.4719 17.06440.1984 0 1 0.25 0 0 16 6 12.1595 7.9605 0.421 15.2223 0.0542 0 0 0 1 016 7 15.144 4.5943 0.5245 18.9647 0.0715 0 0 0 1 0 16 8 12.8343 8.64840.4419 15.9787 0.0561 0 0 0 1 0 16 9 16.3956 11.1135 0.5707 20.63760.0718 0 0 0.25 1 0 16 10 23.2281 7.8585 0.5248 18.9766 0.2155 0 0 0.250 0 16 11 2.8897 2.85 0.1346 4.8679 0.0174 0 0 0 0 0.5 16 12 1.43041.9759 0.0871 3.1485 0.0092 0 0 0 0 0.5 16 13 5.6522 −0.606 0.19467.0353 0.0281 0 0 0 0 0 16 14 17.5895 3.91 0.4404 15.9266 0.167 0 0 0 00 16 15 7.1615 6.6607 0.2719 9.8319 0.0355 0 0 0 0 0 16 16 27.46389.9289 0.7299 26.3922 0.2107 0.1275 0 0 0 0 R C H2MoO4 NH42TiOOX2NH43SbOX3 PtNH32NO22 RuNONO33 SnOX2 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14 0 0.6786 0 0.1275 0 0 0.5714 0 1.3775 13 150.5714 0.6786 0 0.1275 0 0 0 0 1.3775 13 16 0 0 0 0 0 0 0 0 0.1275 14 10 0 0 0.1275 0 0 0 0 1.3775 14 2 0 0 0 0.1275 0 0 0 0.4643 1.3775 14 3 00.4643 0 0.1275 0 0 0 0 1.3775 14 4 0.4643 0 0 0.1275 0 0 0 0 1.3775 145 0 0 0 0.1275 0 0 0 0 1.3775 14 6 0 0 0 0.1275 0 0 0 0.4643 1.3775 14 70 0.4643 0 0.1275 0 0 0 0 1.3775 14 8 0.4643 0 0 0.1275 0 0 0 0 1.377514 9 0 0 0 0.1275 0 0 0 0 1.3775 14 10 0 0 0 0.1275 0 0.7857 0 0 1.377514 11 0 0 0 0.1275 0 0.2321 0 0 0.7525 14 12 0 0 0.2321 0.1275 0 0 0 00.7525 14 13 0 0 0.2321 0.1275 0 0.3929 0 0 0.7525 14 14 0 0.7857 00.1275 0 0 0.4643 0 1.3775 14 15 0.4643 0.7857 0 0.1275 0 0 0 0 1.377514 16 0 0 0 0 0 0 0 0 0 15 1 0 0 0 0.1275 0 0 0 0 1.3775 15 2 0 0 00.1275 0 0 0 0.3571 1.3775 15 3 0 0.3571 0 0.1275 0 0 0 0 1.3775 15 40.3571 0 0 0.1275 0 0 0 0 1.3775 15 5 0 0 0 0.1275 0 0 0 0 1.3775 15 6 00 0 0.1275 0 0 0 0.3571 1.3775 15 7 0 0.3571 0 0.1275 0 0 0 0 1.3775 158 0.3571 0 0 0.1275 0 0 0 0 1.3775 15 9 0 0 0 0.1275 0 0 0 0 1.3775 1510 0 0 0 0.1275 0 0.8929 0 0 1.3775 15 11 0 0 0 0.1275 0 0.1786 0 00.7525 15 12 0 0 0.1786 0.1275 0 0 0 0 0.7525 15 13 0 0 0.1786 0.1275 00.4464 0 0 0.7525 15 14 0 0.8929 0 0.1275 0 0 0.3571 0 1.3775 15 150.3571 0.8929 0 0.1275 0 0 0 0 1.3775 15 16 0 0 0 0 0 0 0 0 0 16 1 0 0 00.1275 0 0 0 0 1.3775 16 2 0 0 0 0.1275 0 0 0 0.25 1.3775 16 3 0 0.25 00.1275 0 0 0 0 1.3775 16 4 0.25 0 0 0.1275 0 0 0 0 1.3775 16 5 0 0 00.1275 0 0 0 0 1.3775 16 6 0 0 0 0.1275 0 0 0 0.25 1.3775 16 7 0 0.25 00.1275 0 0 0 0 1.3775 16 8 0.25 0 0 0.1275 0 0 0 0 1.3775 16 9 0 0 00.1275 0 0 0 0 1.3775 16 10 0 0 0 0.1275 0 1 0 0 1.3775 16 11 0 0 00.1275 0 0.125 0 0 0.7525 16 12 0 0 0.125 0.1275 0 0 0 0 0.7525 16 13 00 0.125 0.1275 0 0.5 0 0 0.7525 16 14 0 1 0 0.1275 0 0 0.25 0 1.3775 1615 0.25 1 0 0.1275 0 0 0 0 1.3775 16 16 0 0 0 0 0 0 0 0 0.1275 R C mol %mol % mol % mol % mol % mol % real real Co mol % Eu Fe mol % Ge Mo mol %Ti Sb mol % Pt Ru mol % Sn V mol % Zr Temperature: 300 C. 1 1 0 0 0 0 00 0 100 0 0 0 0 1 2 0 0 0 0 0 0 0 0 0 0 0 0 1 3 0 0 0 0 0 0 0 0 0 0 0 01 4 0 0 0 0 0 0 0 0 0 0 0 0 1 5 0 0 0 0 0 0 0 0 0 0 0 0 1 6 0 0 0 0 0 00 0 0 0 0 0 1 7 0 0 0 0 0 0 0 100 0 0 0 0 1 8 0 0 0 0 0 0 0 0 0 0 0 0 19 0 0 0 0 0 0 0 0 0 0 0 0 1 10 0 0 0 0 0 0 0 0 0 0 0 0 1 11 0 0 0 0 0 00 0 0 0 0 0 1 12 0 0 0 0 0 0 0 0 0 0 0 0 1 13 0 0 0 0 0 0 0 100 0 0 0 01 14 0 0 0 0 0 0 0 0 0 0 0 0 1 15 0 0 0 0 0 0 0 0 0 0 0 0 1 16 0 0 0 0 00 0 100 0 0 0 0 2 1 18.21 0 72.86 0 0 0 0 0 8.93 0 0 0 2 2 18.21 0 0 0 00 0 0 8.93 0 0 72.86 2 3 18.21 0 0 0 0 72.86 0 0 8.93 0 0 0 2 4 18.21 00 0 72.86 0 0 0 8.93 0 0 0 2 5 18.21 72.86 0 0 0 0 0 0 8.93 0 0 0 2 6 00 18.21 0 0 0 0 0 8.93 0 0 72.86 2 7 0 0 18.21 0 0 72.86 0 0 8.93 0 0 02 8 0 0 18.21 0 72.86 0 0 0 8.93 0 0 0 2 9 0 72.86 18.21 0 0 0 0 0 8.930 0 0 2 10 0 72.86 0 0 0 0 0 0 8.93 18.21 0 0 2 11 0 0 0 16.72 0 0 0 016.39 66.89 0 0 2 12 0 0 0 16.72 0 0 66.89 0 16.39 0 0 0 2 13 0 0 0 0 00 66.89 0 16.39 16.72 0 0 2 14 0 0 0 0 0 18.21 0 0 8.93 0 72.86 0 2 15 00 0 0 72.86 18.21 0 0 8.93 0 0 0 2 16 0 0 0 0 0 0 0 0 0 0 0 0 3 1 27.320 63.75 0 0 0 0 0 8.93 0 0 0 3 2 27.32 0 0 0 0 0 0 0 8.93 0 0 63.75 3 327.32 0 0 0 0 63.75 0 0 8.93 0 0 0 3 4 27.32 0 0 0 63.75 0 0 0 8.93 0 00 3 5 27.32 63.75 0 0 0 0 0 0 8.93 0 0 0 3 6 0 0 27.32 0 0 0 0 0 8.93 00 63.75 3 7 0 0 27.32 0 0 63.75 0 0 8.93 0 0 0 3 8 0 0 27.32 0 63.75 0 00 8.93 0 0 0 3 9 0 63.75 27.32 0 0 0 0 0 8.93 0 0 0 3 10 0 63.75 0 0 0 00 0 8.93 27.32 0 0 3 11 0 0 0 25.08 0 0 0 0 16.39 58.53 0 0 3 12 0 0 025.08 0 0 58.53 0 16.39 0 0 0 3 13 0 0 0 0 0 0 58.53 0 16.39 25.08 0 0 314 0 0 0 0 0 27.32 0 0 8.93 0 63.75 0 3 15 0 0 0 0 63.75 27.32 0 0 8.930 0 0 3 16 0 0 0 0 0 0 0 0 0 0 0 0 4 1 36.43 0 54.64 0 0 0 0 0 8.93 0 00 4 2 36.43 0 0 0 0 0 0 0 8.93 0 0 54.64 4 3 36.43 0 0 0 0 54.64 0 08.93 0 0 0 4 4 36.43 0 0 0 54.64 0 0 0 8.93 0 0 0 4 5 36.43 54.64 0 0 00 0 0 8.93 0 0 0 4 6 0 0 36.43 0 0 0 0 0 8.93 0 0 54.64 4 7 0 0 36.43 00 54.64 0 0 8.93 0 0 0 4 8 0 0 36.43 0 54.64 0 0 0 8.93 0 0 0 4 9 054.64 36.43 0 0 0 0 0 8.93 0 0 0 4 10 0 54.64 0 0 0 0 0 0 8.93 36.43 0 04 11 0 0 0 33.44 0 0 0 0 16.39 50.17 0 0 4 12 0 0 0 33.44 0 0 50.17 016.39 0 0 0 4 13 0 0 0 0 0 0 50.17 0 16.39 33.44 0 0 4 14 0 0 0 0 036.43 0 0 8.93 0 54.64 0 4 15 0 0 0 0 54.64 36.43 0 0 8.93 0 0 0 4 16 00 0 0 0 0 0 100 0 0 0 0 5 1 45.54 0 45.54 0 0 0 0 0 8.93 0 0 0 5 2 45.540 0 0 0 0 0 0 8.93 0 0 45.54 5 3 45.54 0 0 0 0 45.54 0 0 8.93 0 0 0 5 445.54 0 0 0 45.54 0 0 0 8.93 0 0 0 5 5 45.54 45.54 0 0 0 0 0 0 8.93 0 00 5 6 0 0 45.54 0 0 0 0 0 8.93 0 0 45.54 5 7 0 0 45.54 0 0 45.54 0 08.93 0 0 0 5 8 0 0 45.54 0 45.54 0 0 0 8.93 0 0 0 5 9 0 45.54 45.54 0 00 0 0 8.93 0 0 0 5 10 0 45.54 0 0 0 0 0 0 8.93 45.54 0 0 5 11 0 0 041.81 0 0 0 0 16.39 41.81 0 0 5 12 0 0 0 41.81 0 0 41.81 0 16.39 0 0 0 513 0 0 0 0 0 0 41.81 0 16.39 41.81 0 0 5 14 0 0 0 0 0 45.54 0 0 8.93 045.54 0 5 15 0 0 0 0 45.54 45.54 0 0 8.93 0 0 0 5 16 0 0 0 0 0 0 0 0 0 00 0 6 1 54.64 0 36.43 0 0 0 0 0 8.93 0 0 0 6 2 54.64 0 0 0 0 0 0 0 8.930 0 36.43 6 3 54.64 0 0 0 0 36.43 0 0 8.93 0 0 0 6 4 54.64 0 0 0 36.43 00 0 8.93 0 0 0 6 5 54.64 36.43 0 0 0 0 0 0 8.93 0 0 0 6 6 0 0 54.64 0 00 0 0 8.93 0 0 36.43 6 7 0 0 54.64 0 0 36.43 0 0 8.93 0 0 0 6 8 0 054.64 0 36.43 0 0 0 8.93 0 0 0 6 9 0 36.43 54.64 0 0 0 0 0 8.93 0 0 0 610 0 36.43 0 0 0 0 0 0 8.93 54.64 0 0 6 11 0 0 0 50.17 0 0 0 0 16.3933.44 0 0 6 12 0 0 0 50.17 0 0 33.44 0 16.39 0 0 0 6 13 0 0 0 0 0 033.44 0 16.39 50.17 0 0 6 14 0 0 0 0 0 54.64 0 0 8.93 0 36.43 0 6 15 0 00 0 36.43 54.64 0 0 8.93 0 0 0 6 16 0 0 0 0 0 0 0 0 0 0 0 0 7 1 63.75 027.32 0 0 0 0 0 8.93 0 0 0 7 2 63.75 0 0 0 0 0 0 0 8.93 0 0 27.32 7 363.75 0 0 0 0 27.32 0 0 8.93 0 0 0 7 4 63.75 0 0 0 27.32 0 0 0 8.93 0 00 7 5 63.75 27.32 0 0 0 0 0 0 8.93 0 0 0 7 6 0 0 63.75 0 0 0 0 0 8.93 00 27.32 7 7 0 0 63.75 0 0 27.32 0 0 8.93 0 0 0 7 8 0 0 63.75 0 27.32 0 00 8.93 0 0 0 7 9 0 27.32 63.75 0 0 0 0 0 8.93 0 0 0 7 10 0 27.32 0 0 0 00 0 8.93 63.75 0 0 7 11 0 0 0 58.53 0 0 0 0 16.39 25.08 0 0 7 12 0 0 058.53 0 0 25.08 0 16.39 0 0 0 7 13 0 0 0 0 0 0 25.08 0 16.39 58.53 0 0 714 0 0 0 0 0 63.75 0 0 8.93 0 27.32 0 7 15 0 0 0 0 27.32 63.75 0 0 8.930 0 0 7 16 0 0 0 0 0 0 0 100 0 0 0 0 8 1 72.86 0 18.21 0 0 0 0 0 8.93 00 0 8 2 72.86 0 0 0 0 0 0 0 8.93 0 0 18.21 8 3 72.86 0 0 0 0 18.21 0 08.93 0 0 0 8 4 72.86 0 0 0 18.21 0 0 0 8.93 0 0 0 8 5 72.86 18.21 0 0 00 0 0 8.93 0 0 0 8 6 0 0 72.86 0 0 0 0 0 8.93 0 0 18.21 8 7 0 0 72.86 00 18.21 0 0 8.93 0 0 0 8 8 0 0 72.86 0 18.21 0 0 0 8.93 0 0 0 8 9 018.21 72.86 0 0 0 0 0 8.93 0 0 0 8 10 0 18.21 0 0 0 0 0 0 8.93 72.86 0 08 11 0 0 0 66.89 0 0 0 0 16.39 16.72 0 0 8 12 0 0 0 66.89 0 0 16.72 016.39 0 0 0 8 13 0 0 0 0 0 0 16.72 0 16.39 66.89 0 0 8 14 0 0 0 0 072.86 0 0 8.93 0 18.21 0 8 15 0 0 0 0 18.21 72.86 0 0 8.93 0 0 0 8 16 00 0 0 0 0 0 0 0 0 0 0 9 1 18.15 0 72.6 0 0 0 0 9.26 0 0 0 0 9 2 18.15 00 0 0 0 0 9.26 0 0 0 72.6 9 3 18.15 0 0 0 0 72.6 0 9.26 0 0 0 0 9 418.15 0 0 0 72.6 0 0 9.26 0 0 0 0 9 5 18.15 72.6 0 0 0 0 0 9.26 0 0 0 09 6 0 0 18.15 0 0 0 0 9.26 0 0 0 72.6 9 7 0 0 18.15 0 0 72.6 0 9.26 0 00 0 9 8 0 0 18.15 0 72.6 0 0 9.26 0 0 0 0 9 9 0 72.6 18.15 0 0 0 0 9.260 0 0 0 9 10 0 72.6 0 0 0 0 0 9.26 0 18.15 0 0 9 11 0 0 0 16.61 0 0 016.94 0 66.45 0 0 9 12 0 0 0 16.61 0 0 66.45 16.94 0 0 0 0 9 13 0 0 0 00 0 66.45 16.94 0 16.61 0 0 9 14 0 0 0 0 0 18.15 0 9.26 0 0 72.6 0 9 150 0 0 0 72.6 18.15 0 9.26 0 0 0 0 9 16 0 0 0 0 0 0 0 0 0 0 0 0 10 125.93 0 64.82 0 0 0 0 9.26 0 0 0 0 10 2 25.93 0 0 0 0 0 0 9.26 0 0 064.82 10 3 25.93 0 0 0 0 64.82 0 9.26 0 0 0 0 10 4 25.93 0 0 0 64.82 0 09.26 0 0 0 0 10 5 25.93 64.82 0 0 0 0 0 9.26 0 0 0 0 10 6 0 0 25.93 0 00 0 9.26 0 0 0 64.82 10 7 0 0 25.93 0 0 64.82 0 9.26 0 0 0 0 10 8 0 025.93 0 64.82 0 0 9.26 0 0 0 0 10 9 0 64.82 25.93 0 0 0 0 9.26 0 0 0 010 10 0 64.82 0 0 0 0 0 9.26 0 25.93 0 0 10 11 0 0 0 23.73 0 0 0 16.94 059.33 0 0 10 12 0 0 0 23.73 0 0 59.33 16.94 0 0 0 0 10 13 0 0 0 0 0 059.33 16.94 0 23.73 0 0 10 14 0 0 0 0 0 25.93 0 9.26 0 0 64.82 0 10 15 00 0 0 64.82 25.93 0 9.26 0 0 0 0 10 16 0 0 0 0 0 0 0 100 0 0 0 0 11 133.7 0 57.04 0 0 0 0 9.26 0 0 0 0 11 2 33.7 0 0 0 0 0 0 9.26 0 0 0 57.0411 3 33.7 0 0 0 0 57.04 0 9.26 0 0 0 0 11 4 33.7 0 0 0 57.04 0 0 9.26 00 0 0 11 5 33.7 57.04 0 0 0 0 0 9.26 0 0 0 0 11 6 0 0 33.7 0 0 0 0 9.260 0 0 57.04 11 7 0 0 33.7 0 0 57.04 0 9.26 0 0 0 0 11 8 0 0 33.7 0 57.040 0 9.26 0 0 0 0 11 9 0 57.04 33.7 0 0 0 0 9.26 0 0 0 0 11 10 0 57.04 00 0 0 0 9.26 0 33.7 0 0 11 11 0 0 0 30.85 0 0 0 16.94 0 52.21 0 0 11 120 0 0 30.85 0 0 52.21 16.94 0 0 0 0 11 13 0 0 0 0 0 0 52.21 16.94 030.85 0 0 11 14 0 0 0 0 0 33.7 0 9.26 0 0 57.04 0 11 15 0 0 0 0 57.0433.7 0 9.26 0 0 0 0 11 16 0 0 0 0 0 0 0 0 0 0 0 0 12 1 41.48 0 49.26 0 00 0 9.26 0 0 0 0 12 2 41.48 0 0 0 0 0 0 9.26 0 0 0 49.26 12 3 41.48 0 00 0 49.26 0 9.26 0 0 0 0 12 4 41.48 0 0 0 49.26 0 0 9.26 0 0 0 0 12 541.48 49.26 0 0 0 0 0 9.26 0 0 0 0 12 6 0 0 41.48 0 0 0 0 9.26 0 0 049.26 12 7 0 0 41.48 0 0 49.26 0 9.26 0 0 0 0 12 8 0 0 41.48 0 49.26 0 09.26 0 0 0 0 12 9 0 49.26 41.48 0 0 0 0 9.26 0 0 0 0 12 10 0 49.26 0 0 00 0 9.26 0 41.48 0 0 12 11 0 0 0 37.97 0 0 0 16.94 0 45.09 0 0 12 12 0 00 37.97 0 0 45.09 16.94 0 0 0 0 12 13 0 0 0 0 0 0 45.09 16.94 0 37.97 00 12 14 0 0 0 0 0 41.48 0 9.26 0 0 49.26 0 12 15 0 0 0 0 49.26 41.48 09.26 0 0 0 0 12 16 0 0 0 0 0 0 0 0 0 0 0 0 13 1 49.26 0 41.48 0 0 0 09.26 0 0 0 0 13 2 49.26 0 0 0 0 0 0 9.26 0 0 0 41.48 13 3 49.26 0 0 0 041.48 0 9.26 0 0 0 0 13 4 49.26 0 0 0 41.48 0 0 9.26 0 0 0 0 13 5 49.2641.48 0 0 0 0 0 9.26 0 0 0 0 13 6 0 0 49.26 0 0 0 0 9.26 0 0 0 41.48 137 0 0 49.26 0 0 41.48 0 9.26 0 0 0 0 13 8 0 0 49.26 0 41.48 0 0 9.26 0 00 0 13 9 0 41.48 49.26 0 0 0 0 9.26 0 0 0 0 13 10 0 41.48 0 0 0 0 0 9.260 49.26 0 0 13 11 0 0 0 45.09 0 0 0 16.94 0 37.97 0 0 13 12 0 0 0 45.090 0 37.97 16.94 0 0 0 0 13 13 0 0 0 0 0 0 37.97 16.94 0 45.09 0 0 13 140 0 0 0 0 49.26 0 9.26 0 0 41.48 0 13 15 0 0 0 0 41.48 49.26 0 9.26 0 00 0 13 16 0 0 0 0 0 0 0 100 0 0 0 0 14 1 57.04 0 33.7 0 0 0 0 9.26 0 0 00 14 2 57.04 0 0 0 0 0 0 9.26 0 0 0 33.7 14 3 57.04 0 0 0 0 33.7 0 9.260 0 0 0 14 4 57.04 0 0 0 33.7 0 0 9.26 0 0 0 0 14 5 57.04 33.7 0 0 0 0 09.26 0 0 0 0 14 6 0 0 57.04 0 0 0 0 9.26 0 0 0 33.7 14 7 0 0 57.04 0 033.7 0 9.26 0 0 0 0 14 8 0 0 57.04 0 33.7 0 0 9.26 0 0 0 0 14 9 0 33.757.04 0 0 0 0 9.26 0 0 0 0 14 10 0 33.7 0 0 0 0 0 9.26 0 57.04 0 0 14 110 0 0 52.21 0 0 0 16.94 0 30.85 0 0 14 12 0 0 0 52.21 0 0 30.85 16.94 00 0 0 14 13 0 0 0 0 0 0 30.85 16.94 0 52.21 0 0 14 14 0 0 0 0 0 57.04 09.26 0 0 33.7 0 14 15 0 0 0 0 33.7 57.04 0 9.26 0 0 0 0 14 16 0 0 0 0 00 0 0 0 0 0 0 15 1 64.82 0 25.93 0 0 0 0 9.26 0 0 0 0 15 2 64.82 0 0 0 00 0 9.26 0 0 0 25.93 15 3 64.82 0 0 0 0 25.93 0 9.26 0 0 0 0 15 4 64.820 0 0 25.93 0 0 9.26 0 0 0 0 15 5 64.82 25.93 0 0 0 0 0 9.26 0 0 0 0 156 0 0 64.82 0 0 0 0 9.26 0 0 0 25.93 15 7 0 0 64.82 0 0 25.93 0 9.26 0 00 0 15 8 0 0 64.82 0 25.93 0 0 9.26 0 0 0 0 15 9 0 25.93 64.82 0 0 0 09.26 0 0 0 0 15 10 0 25.93 0 0 0 0 0 9.26 0 64.82 0 0 15 11 0 0 0 59.330 0 0 16.94 0 23.73 0 0 15 12 0 0 0 59.33 0 0 23.73 16.94 0 0 0 0 15 130 0 0 0 0 0 23.73 16.94 0 59.33 0 0 15 14 0 0 0 0 0 64.82 0 9.26 0 025.93 0 15 15 0 0 0 0 25.93 64.82 0 9.26 0 0 0 0 15 16 0 0 0 0 0 0 0 0 00 0 0 16 1 72.6 0 18.15 0 0 0 0 9.26 0 0 0 0 16 2 72.6 0 0 0 0 0 0 9.260 0 0 18.15 16 3 72.6 0 0 0 0 18.15 0 9.26 0 0 0 0 16 4 72.6 0 0 0 18.150 0 9.26 0 0 0 0 16 5 72.6 18.15 0 0 0 0 0 9.26 0 0 0 0 16 6 0 0 72.6 00 0 0 9.26 0 0 0 18.15 16 7 0 0 72.6 0 0 18.15 0 9.26 0 0 0 0 16 8 0 072.6 0 18.15 0 0 9.26 0 0 0 0 16 9 0 18.15 72.6 0 0 0 0 9.26 0 0 0 0 1610 0 18.15 0 0 0 0 0 9.26 0 72.6 0 0 16 11 0 0 0 66.45 0 0 0 16.94 016.61 0 0 16 12 0 0 0 66.45 0 0 16.61 16.94 0 0 0 0 16 13 0 0 0 0 0 016.61 16.94 0 66.45 0 0 16 14 0 0 0 0 0 72.6 0 9.26 0 0 18.15 0 16 15 00 0 0 18.15 72.6 0 9.26 0 0 0 0 16 16 0 0 0 0 0 0 0 100 0 0 0 0Temperature: 350 C. 1 0 1 0 0 0 0 0 0 100 0 0 0 0 1 2 0 0 0 0 0 0 0 0 00 0 0 1 3 0 0 0 0 0 0 0 0 0 0 0 0 1 4 0 0 0 0 0 0 0 0 0 0 0 0 1 5 0 0 00 0 0 0 0 0 0 0 0 1 6 0 0 0 0 0 0 0 0 0 0 0 0 1 7 0 0 0 0 0 0 0 100 0 00 0 1 8 0 0 0 0 0 0 0 0 0 0 0 0 1 9 0 0 0 0 0 0 0 0 0 0 0 0 1 10 0 0 0 00 0 0 0 0 0 0 0 1 11 0 0 0 0 0 0 0 0 0 0 0 0 1 12 0 0 0 0 0 0 0 0 0 0 00 1 13 0 0 0 0 0 0 0 100 0 0 0 0 1 14 0 0 0 0 0 0 0 0 0 0 0 0 1 15 0 0 00 0 0 0 0 0 0 0 0 1 16 0 0 0 0 0 0 0 100 0 0 0 0 2 1 18.21 0 72.86 0 0 00 0 8.93 0 0 0 2 2 18.21 0 0 0 0 0 0 0 8.93 0 0 72.86 2 3 18.21 0 0 0 072.86 0 0 8.93 0 0 0 2 4 18.21 0 0 0 72.86 0 0 0 8.93 0 0 0 2 5 18.2172.86 0 0 0 0 0 0 8.93 0 0 0 2 6 0 0 18.21 0 0 0 0 0 8.93 0 0 72.86 2 70 0 18.21 0 0 72.86 0 0 8.93 0 0 0 2 8 0 0 18.21 0 72.86 0 0 0 8.93 0 00 2 9 0 72.86 18.21 0 0 0 0 0 8.93 0 0 0 2 10 0 72.86 0 0 0 0 0 0 8.9318.21 0 0 2 11 0 0 0 16.72 0 0 0 0 16.39 66.89 0 0 2 12 0 0 0 16.72 0 066.89 0 16.39 0 0 0 2 13 0 0 0 0 0 0 66.89 0 16.39 16.72 0 0 2 14 0 0 00 0 18.21 0 0 8.93 0 72.86 0 2 15 0 0 0 0 72.86 18.21 0 0 8.93 0 0 0 216 0 0 0 0 0 0 0 0 0 0 0 0 3 1 27.32 0 63.75 0 0 0 0 0 8.93 0 0 0 3 227.32 0 0 0 0 0 0 0 8.93 0 0 63.75 3 3 27.32 0 0 0 0 63.75 0 0 8.93 0 00 3 4 27.32 0 0 0 63.75 0 0 0 8.93 0 0 0 3 5 27.32 63.75 0 0 0 0 0 08.93 0 0 0 3 6 0 0 27.32 0 0 0 0 0 8.93 0 0 63.75 3 7 0 0 27.32 0 063.75 0 0 8.93 0 0 0 3 8 0 0 27.32 0 63.75 0 0 0 8.93 0 0 0 3 9 0 63.7527.32 0 0 0 0 0 8.93 0 0 0 3 10 0 63.75 0 0 0 0 0 0 8.93 27.32 0 0 3 110 0 0 25.08 0 0 0 0 16.39 58.53 0 0 3 12 0 0 0 25.08 0 0 58.53 0 16.39 00 0 3 13 0 0 0 0 0 0 58.53 0 16.39 25.08 0 0 3 14 0 0 0 0 0 27.32 0 08.93 0 63.75 0 3 15 0 0 0 0 63.75 27.32 0 0 8.93 0 0 0 3 16 0 0 0 0 0 00 0 0 0 0 0 4 1 36.43 0 54.64 0 0 0 0 0 8.93 0 0 0 4 2 36.43 0 0 0 0 0 00 8.93 0 0 54.64 4 3 36.43 0 0 0 0 54.64 0 0 8.93 0 0 0 4 4 36.43 0 0 054.64 0 0 0 8.93 0 0 0 4 5 36.43 54.64 0 0 0 0 0 0 8.93 0 0 0 4 6 0 036.43 0 0 0 0 0 8.93 0 0 54.64 4 7 0 0 36.43 0 0 54.64 0 0 8.93 0 0 0 48 0 0 36.43 0 54.64 0 0 0 8.93 0 0 0 4 9 0 54.64 36.43 0 0 0 0 0 8.93 00 0 4 10 0 54.64 0 0 0 0 0 0 8.93 36.43 0 0 4 11 0 0 0 33.44 0 0 0 016.39 50.17 0 0 4 12 0 0 0 33.44 0 0 50.17 0 16.39 0 0 0 4 13 0 0 0 0 00 50.17 0 16.39 33.44 0 0 4 14 0 0 0 0 0 36.43 0 0 8.93 0 54.64 0 4 15 00 0 0 54.64 36.43 0 0 8.93 0 0 0 4 16 0 0 0 0 0 0 0 100 0 0 0 0 5 145.54 0 45.54 0 0 0 0 0 8.93 0 0 0 5 2 45.54 0 0 0 0 0 0 0 8.93 0 045.54 5 3 45.54 0 0 0 0 45.54 0 0 8.93 0 0 0 5 4 45.54 0 0 0 45.54 0 0 08.93 0 0 0 5 5 45.54 45.54 0 0 0 0 0 0 8.93 0 0 0 5 6 0 0 45.54 0 0 0 00 8.93 0 0 45.54 5 7 0 0 45.54 0 0 45.54 0 0 8.93 0 0 0 5 8 0 0 45.54 045.54 0 0 0 8.93 0 0 0 5 9 0 45.54 45.54 0 0 0 0 0 8.93 0 0 0 5 10 045.54 0 0 0 0 0 0 8.93 45.54 0 0 5 11 0 0 0 41.81 0 0 0 0 16.39 41.81 00 5 12 0 0 0 41.81 0 0 41.81 0 16.39 0 0 0 5 13 0 0 0 0 0 0 41.81 016.39 41.81 0 0 5 14 0 0 0 0 0 45.54 0 0 8.93 0 45.54 0 5 15 0 0 0 045.54 45.54 0 0 8.93 0 0 0 5 16 0 0 0 0 0 0 0 0 0 0 0 0 6 1 54.64 036.43 0 0 0 0 0 8.93 0 0 0 6 2 54.64 0 0 0 0 0 0 0 8.93 0 0 36.43 6 354.64 0 0 0 0 36.43 0 0 8.93 0 0 0 6 4 54.64 0 0 0 36.43 0 0 0 8.93 0 00 6 5 54.64 36.43 0 0 0 0 0 0 8.93 0 0 0 6 6 0 0 54.64 0 0 0 0 0 8.93 00 36.43 6 7 0 0 54.64 0 0 36.43 0 0 8.93 0 0 0 6 8 0 0 54.64 0 36.43 0 00 8.93 0 0 0 6 9 0 36.43 54.64 0 0 0 0 0 8.93 0 0 0 6 10 0 36.43 0 0 0 00 0 8.93 54.64 0 0 6 11 0 0 0 50.17 0 0 0 0 16.39 33.44 0 0 6 12 0 0 050.17 0 0 33.44 0 16.39 0 0 0 6 13 0 0 0 0 0 0 33.44 0 16.39 50.17 0 0 614 0 0 0 0 0 54.64 0 0 8.93 0 36.43 0 6 15 0 0 0 0 36.43 54.64 0 0 8.930 0 0 6 16 0 0 0 0 0 0 0 0 0 0 0 0 7 1 63.75 0 27.32 0 0 0 0 0 8.93 0 00 7 2 63.75 0 0 0 0 0 0 0 8.93 0 0 27.32 7 3 63.75 0 0 0 0 27.32 0 08.93 0 0 0 7 4 63.75 0 0 0 27.32 0 0 0 8.93 0 0 0 7 5 63.75 27.32 0 0 00 0 0 8.93 0 0 0 7 6 0 0 63.75 0 0 0 0 0 8.93 0 0 27.32 7 7 0 0 63.75 00 27.32 0 0 8.93 0 0 0 7 8 0 0 63.75 0 27.32 0 0 0 8.93 0 0 0 7 9 027.32 63.75 0 0 0 0 0 8.93 0 0 0 7 10 0 27.32 0 0 0 0 0 0 8.93 63.75 0 07 11 0 0 0 58.53 0 0 0 0 16.39 25.08 0 0 7 12 0 0 0 58.53 0 0 25.08 016.39 0 0 0 7 13 0 0 0 0 0 0 25.08 0 16.39 58.53 0 0 7 14 0 0 0 0 063.75 0 0 8.93 0 27.32 0 7 15 0 0 0 0 27.32 63.75 0 0 8.93 0 0 0 7 16 00 0 0 0 0 0 100 0 0 0 0 8 1 72.86 0 18.21 0 0 0 0 0 8.93 0 0 0 8 2 72.860 0 0 0 0 0 0 8.93 0 0 18.21 8 3 72.86 0 0 0 0 18.21 0 0 8.93 0 0 0 8 472.86 0 0 0 18.21 0 0 0 8.93 0 0 0 8 5 72.86 18.21 0 0 0 0 0 0 8.93 0 00 8 6 0 0 72.86 0 0 0 0 0 8.93 0 0 18.21 8 7 0 0 72.86 0 0 18.21 0 08.93 0 0 0 8 8 0 0 72.86 0 18.21 0 0 0 8.93 0 0 0 8 9 0 18.21 72.86 0 00 0 0 8.93 0 0 0 8 10 0 18.21 0 0 0 0 0 0 8.93 72.86 0 0 8 11 0 0 066.89 0 0 0 0 16.39 16.72 0 0 8 12 0 0 0 66.89 0 0 16.72 0 16.39 0 0 0 813 0 0 0 0 0 0 16.72 0 16.39 66.89 0 0 8 14 0 0 0 0 0 72.86 0 0 8.93 018.21 0 8 15 0 0 0 0 18.21 72.86 0 0 8.93 0 0 0 8 16 0 0 0 0 0 0 0 0 0 00 0 9 1 18.15 0 72.6 0 0 0 0 9.26 0 0 0 0 9 2 18.15 0 0 0 0 0 0 9.26 0 00 72.6 9 3 18.15 0 0 0 0 72.6 0 9.26 0 0 0 0 9 4 18.15 0 0 0 72.6 0 09.26 0 0 0 0 9 5 18.15 72.6 0 0 0 0 0 9.26 0 0 0 0 9 6 0 0 18.15 0 0 0 09.26 0 0 0 72.6 9 7 0 0 18.15 0 0 72.6 0 9.26 0 0 0 0 9 8 0 0 18.15 072.6 0 0 9.26 0 0 0 0 9 9 0 72.6 18.15 0 0 0 0 9.26 0 0 0 0 9 10 0 72.60 0 0 0 0 9.26 0 18.15 0 0 9 11 0 0 0 16.61 0 0 0 16.94 0 66.45 0 0 9 120 0 0 16.61 0 0 66.45 16.94 0 0 0 0 9 13 0 0 0 0 0 0 66.45 16.94 0 16.610 0 9 14 0 0 0 0 0 18.15 0 9.26 0 0 72.6 0 9 15 0 0 0 0 72.6 18.15 09.26 0 0 0 0 9 16 0 0 0 0 0 0 0 0 0 0 0 0 10 1 25.93 0 64.82 0 0 0 09.26 0 0 0 0 10 2 25.93 0 0 0 0 0 0 9.26 0 0 0 64.82 10 3 25.93 0 0 0 064.82 0 9.26 0 0 0 0 10 4 25.93 0 0 0 64.82 0 0 9.26 0 0 0 0 10 5 25.9364.82 0 0 0 0 0 9.26 0 0 0 0 10 6 0 0 25.93 0 0 0 0 9.26 0 0 0 64.82 107 0 0 25.93 0 0 64.82 0 9.26 0 0 0 0 10 8 0 0 25.93 0 64.82 0 0 9.26 0 00 0 10 9 0 64.82 25.93 0 0 0 0 9.26 0 0 0 0 10 10 0 64.82 0 0 0 0 0 9.260 25.93 0 0 10 11 0 0 0 23.73 0 0 0 16.94 0 59.33 0 0 10 12 0 0 0 23.730 0 59.33 16.94 0 0 0 0 10 13 0 0 0 0 0 0 59.33 16.94 0 23.73 0 0 10 140 0 0 0 0 25.93 0 9.26 0 0 64.82 0 10 15 0 0 0 0 64.82 25.93 0 9.26 0 00 0 10 16 0 0 0 0 0 0 0 100 0 0 0 0 11 1 33.7 0 57.04 0 0 0 0 9.26 0 0 00 11 2 33.7 0 0 0 0 0 0 9.26 0 0 0 57.04 11 3 33.7 0 0 0 0 57.04 0 9.260 0 0 0 11 4 33.7 0 0 0 57.04 0 0 9.26 0 0 0 0 11 5 33.7 57.04 0 0 0 0 09.26 0 0 0 0 11 6 0 0 33.7 0 0 0 0 9.26 0 0 0 57.04 11 7 0 0 33.7 0 057.04 0 9.26 0 0 0 0 11 8 0 0 33.7 0 57.04 0 0 9.26 0 0 0 0 11 9 0 57.0433.7 0 0 0 0 9.26 0 0 0 0 11 10 0 57.04 0 0 0 0 0 9.26 0 33.7 0 0 11 110 0 0 30.85 0 0 0 16.94 0 52.21 0 0 11 12 0 0 0 30.85 0 0 52.21 16.94 00 0 0 11 13 0 0 0 0 0 0 52.21 16.94 0 30.85 0 0 11 14 0 0 0 0 0 33.7 09.26 0 0 57.04 0 11 15 0 0 0 0 57.04 33.7 0 9.26 0 0 0 0 11 16 0 0 0 0 00 0 0 0 0 0 0 12 1 41.48 0 49.26 0 0 0 0 9.26 0 0 0 0 12 2 41.48 0 0 0 00 0 9.26 0 0 0 49.26 12 3 41.48 0 0 0 0 49.26 0 9.26 0 0 0 0 12 4 41.480 0 0 49.26 0 0 9.26 0 0 0 0 12 5 41.48 49.26 0 0 0 0 0 9.26 0 0 0 0 126 0 0 41.48 0 0 0 0 9.26 0 0 0 49.26 12 7 0 0 41.48 0 0 49.26 0 9.26 0 00 0 12 8 0 0 41.48 0 49.26 0 0 9.26 0 0 0 0 12 9 0 49.26 41.48 0 0 0 09.26 0 0 0 0 12 10 0 49.26 0 0 0 0 0 9.26 0 41.48 0 0 12 11 0 0 0 37.970 0 0 16.94 0 45.09 0 0 12 12 0 0 0 37.97 0 0 45.09 16.94 0 0 0 0 12 130 0 0 0 0 0 45.09 16.94 0 37.97 0 0 12 14 0 0 0 0 0 41.48 0 9.26 0 049.26 0 12 15 0 0 0 0 49.26 41.48 0 9.26 0 0 0 0 12 16 0 0 0 0 0 0 0 0 00 0 0 13 1 49.26 0 41.48 0 0 0 0 9.26 0 0 0 0 13 2 49.26 0 0 0 0 0 09.26 0 0 0 41.48 13 3 49.26 0 0 0 0 41.48 0 9.26 0 0 0 0 13 4 49.26 0 00 41.48 0 0 9.26 0 0 0 0 13 5 49.26 41.48 0 0 0 0 0 9.26 0 0 0 0 13 6 00 49.26 0 0 0 0 9.26 0 0 0 41.48 13 7 0 0 49.26 0 0 41.48 0 9.26 0 0 0 013 8 0 0 49.26 0 41.48 0 0 9.26 0 0 0 0 13 9 0 41.48 49.26 0 0 0 0 9.260 0 0 0 13 10 0 41.48 0 0 0 0 0 9.26 0 49.26 0 0 13 11 0 0 0 45.09 0 0 016.94 0 37.97 0 0 13 12 0 0 0 45.09 0 0 37.97 16.94 0 0 0 0 13 13 0 0 00 0 0 37.97 16.94 0 45.09 0 0 13 14 0 0 0 0 0 49.26 0 9.26 0 0 41.48 013 15 0 0 0 0 41.48 49.26 0 9.26 0 0 0 0 13 16 0 0 0 0 0 0 0 100 0 0 0 014 1 57.04 0 33.7 0 0 0 0 9.26 0 0 0 0 14 2 57.04 0 0 0 0 0 0 9.26 0 0 033.7 14 3 57.04 0 0 0 0 33.7 0 9.26 0 0 0 0 14 4 57.04 0 0 0 33.7 0 09.26 0 0 0 0 14 5 57.04 33.7 0 0 0 0 0 9.26 0 0 0 0 14 6 0 0 57.04 0 0 00 9.26 0 0 0 33.7 14 7 0 0 57.04 0 0 33.7 0 9.26 0 0 0 0 14 8 0 0 57.040 33.7 0 0 9.26 0 0 0 0 14 9 0 33.7 57.04 0 0 0 0 9.26 0 0 0 0 14 10 033.7 0 0 0 0 0 9.26 0 57.04 0 0 14 11 0 0 0 52.21 0 0 0 16.94 0 30.85 00 14 12 0 0 0 52.21 0 0 30.85 16.94 0 0 0 0 14 13 0 0 0 0 0 0 30.8516.94 0 52.21 0 0 14 14 0 0 0 0 0 57.04 0 9.26 0 0 33.7 0 14 15 0 0 0 033.7 57.04 0 9.26 0 0 0 0 14 16 0 0 0 0 0 0 0 0 0 0 0 0 15 1 64.82 025.93 0 0 0 0 9.26 0 0 0 0 15 2 64.82 0 0 0 0 0 0 9.26 0 0 0 25.93 15 364.82 0 0 0 0 25.93 0 9.26 0 0 0 0 15 4 64.82 0 0 0 25.93 0 0 9.26 0 0 00 15 5 64.82 25.93 0 0 0 0 0 9.26 0 0 0 0 15 6 0 0 64.82 0 0 0 0 9.26 00 0 25.93 15 7 0 0 64.82 0 0 25.93 0 9.26 0 0 0 0 15 8 0 0 64.82 0 25.930 0 9.26 0 0 0 0 15 9 0 25.93 64.82 0 0 0 0 9.26 0 0 0 0 15 10 0 25.93 00 0 0 0 9.26 0 64.82 0 0 15 11 0 0 0 59.33 0 0 0 16.94 0 23.73 0 0 15 120 0 0 59.33 0 0 23.73 16.94 0 0 0 0 15 13 0 0 0 0 0 0 23.73 16.94 059.33 0 0 15 14 0 0 0 0 0 64.82 0 9.26 0 0 25.93 0 15 15 0 0 0 0 25.9364.82 0 9.26 0 0 0 0 15 16 0 0 0 0 0 0 0 0 0 0 0 0 16 1 72.6 0 18.15 0 00 0 9.26 0 0 0 0 16 2 72.6 0 0 0 0 0 0 9.26 0 0 0 18.15 16 3 72.6 0 0 00 18.15 0 9.26 0 0 0 0 16 4 72.6 0 0 0 18.15 0 0 9.26 0 0 0 0 16 5 72.618.15 0 0 0 0 0 9.26 0 0 0 0 16 6 0 0 72.6 0 0 0 0 9.26 0 0 0 18.15 16 70 0 72.6 0 0 18.15 0 9.26 0 0 0 0 16 8 0 0 72.6 0 18.15 0 0 9.26 0 0 0 016 9 0 18.15 72.6 0 0 0 0 9.26 0 0 0 0 16 10 0 18.15 0 0 0 0 0 9.26 072.6 0 0 16 11 0 0 0 66.45 0 0 0 16.94 0 16.61 0 0 16 12 0 0 0 66.45 0 016.61 16.94 0 0 0 0 16 13 0 0 0 0 0 0 16.61 16.94 0 66.45 0 0 16 14 0 00 0 0 72.6 0 9.26 0 0 18.15 0 16 15 0 0 0 0 18.15 72.6 0 9.26 0 0 0 0 1616 0 0 0 0 0 0 100 0 0 0 0 0

TABLE II R C COCONV H2OCONV CO2PROD CO2PERPROD CH4PROD Pt1.0%/ZrO2_stdLaNO33 PtNH32NO22 ZrONO32 real real real real real real real real realreal real SUM_micromols mol % La mol % Pt mol % Zr Temperature: 250 C. 11 24.0554 20.3567 1.0059 36.8713 0.1785 0.1275 0 0 0 0.1275 0 100 0 1 2−1.7201 3.3539 0.049 1.7972 0.0067 0 0 0 0 0 0 0 0 1 3 −1.3278 2.24990.0009 0.0315 −0.0026 0 0 0 0 0 0 0 0 1 4 −1.208 2.4958 0.005 0.1823−0.0038 0 0 0 0 0 0 0 0 1 5 −1.3966 −0.6647 0.0138 0.5067 −0.0024 0 0 00 0 0 0 0 1 6 −0.857 −0.806 0.0089 0.3249 −0.0058 0 0 0 0 0 0 0 0 1 726.8747 16.7142 0.9416 34.513 0.151 0.1275 0 0 0 0.1275 0 100 0 1 8−0.1762 0.0001 0.0106 0.3868 −0.0076 0 0 0 0 0 0 0 0 1 9 −0.605 −1.40540.0016 0.0598 −0.0081 0 0 0 0 0 0 0 0 1 10 −0.1705 5.1803 −0.0005−0.0171 −0.0108 0 0 0 0 0 0 0 0 1 11 0.0287 −2.3403 −0.0261 −0.9568−0.0134 0 0 0 0 0 0 0 0 1 12 −0.3619 −2.3753 −0.0191 −0.6997 −0.0107 0 00 0 0 0 0 0 1 13 26.9134 15.6985 0.9206 33.7449 0.1456 0.1275 0 0 00.1275 0 100 0 1 14 0.2866 −1.4436 0.0104 0.3794 −0.0009 0 0 0 0 0 0 0 01 15 −0.2691 −2.5021 −0.0098 −0.3592 −0.0125 0 0 0 0 0 0 0 0 1 1626.3015 15.0776 0.9071 33.2485 0.1422 0.1275 0 0 0 0.1275 0 100 0 2 110.3797 7.5635 0.2714 9.9469 0.0465 0 0 0.0319 0 0.0319 0 100 0 2 222.2742 13.6256 0.7038 25.7961 0.1014 0 0 0.0319 0 0.0319 0 100 0 2 320.1518 11.8043 0.6181 22.6557 0.0925 0 0 0.0319 0 0.0319 0 100 0 2 414.7068 7.5278 0.4396 16.1127 0.074 0 0 0.0319 0 0.0319 0 100 0 2 512.5748 6.9812 0.3538 12.9691 0.0619 0 0 0.0319 0 0.0319 0 100 0 2 612.5733 7.5902 0.3721 13.6375 0.065 0 0 0.0319 0 0.0319 0 100 0 2 73.9682 1.1157 0.1053 3.861 0.0291 0 0 0.0319 0 0.0319 0 100 0 2 8 4.29021.5276 0.1017 3.728 0.0316 0 0 0.0319 0 0.0319 0 100 0 2 9 17.58599.8527 0.5611 20.5685 0.0868 0 0 0.0319 0 0.0319 0 100 0 2 10 4.00560.7967 0.1073 3.9343 0.0337 0 0 0.0319 0 0.0319 0 100 0 2 11 0.4511−1.4852 −0.0262 −0.9611 0.0142 0 0 0.0319 0 0.0319 0 100 0 2 12 8.75153.1358 0.2704 9.9096 0.0534 0 0 0.0319 0 0.0319 0 100 0 2 13 1.1667−0.4291 0.0028 0.1022 0.0172 0 0 0.0319 0 0.0319 0 100 0 2 14 5.37883.039 0.1661 6.0891 0.0402 0 0 0.0319 0.625 0.6569 0 4.85 95.15 2 1513.8175 7.9862 0.4538 16.6329 0.0753 0 0.625 0.0319 0 0.6569 95.15 4.850 2 16 0.5892 0.0397 −0.0171 −0.6274 −0.0021 0 0 0 0 0 0 0 0 3 1 23.034114.9411 0.7335 26.8867 0.1082 0 0 0.0387 0 0.0387 0 100 0 3 2 24.826816.0912 0.7611 27.8973 0.108 0 0 0.0387 0 0.0387 0 100 0 3 3 21.031212.2163 0.6617 24.2545 0.0974 0 0 0.0387 0 0.0387 0 100 0 3 4 15.30628.5994 0.4563 16.7247 0.0714 0 0 0.0387 0 0.0387 0 100 0 3 5 13.18186.4699 0.3775 13.8381 0.0651 0 0 0.0387 0 0.0387 0 100 0 3 6 14.47789.2713 0.4241 15.5437 0.0643 0 0 0.0387 0 0.0387 0 100 0 3 7 5.57173.3425 0.1029 3.772 0.0251 0 0 0.0387 0 0.0387 0 100 0 3 8 6.8228 1.69230.1521 5.5733 0.0283 0 0 0.0387 0 0.0387 0 100 0 3 9 18.2423 12.16780.5606 20.5468 0.0831 0 0 0.0387 0 0.0387 0 100 0 3 10 6.7011 5.58570.1612 5.907 0.033 0 0 0.0387 0 0.0387 0 100 0 3 11 1.3529 1.3312−0.0328 −1.2024 0.0065 0 0 0.0387 0 0.0387 0 100 0 3 12 8.988 6.94540.2544 9.3233 0.0421 0 0 0.0387 0 0.0387 0 100 0 3 13 1.9882 1.6201−0.0124 −0.4561 0.0102 0 0 0.0387 0 0.0387 0 100 0 3 14 6.7207 4.88020.1283 4.7036 0.0288 0 0 0.0387 0.625 0.6637 0 5.83 94.17 3 15 13.12547.8413 0.4144 15.1912 0.0623 0 0.625 0.0387 0 0.6637 94.17 5.83 0 3 161.6968 −0.6116 −0.0065 −0.238 0.007 0 0 0 0 0 0 0 0 4 1 25.6701 19.51970.7514 27.5411 0.0986 0 0 0.0455 0 0.0455 0 100 0 4 2 23.653 16.92270.7928 29.0607 0.0984 0 0 0.0455 0 0.0455 0 100 0 4 3 22.8118 16.18440.6593 24.168 0.0919 0 0 0.0455 0 0.0455 0 100 0 4 4 16.4182 10.78730.4837 17.731 0.0754 0 0 0.0455 0 0.0455 0 100 0 4 5 14.5564 7.51370.4146 15.1965 0.0579 0 0 0.0455 0 0.0455 0 100 0 4 6 15.7933 9.82730.453 16.6027 0.0657 0 0 0.0455 0 0.0455 0 100 0 4 7 6.1716 5.31920.1362 4.9935 0.0244 0 0 0.0455 0 0.0455 0 100 0 4 8 7.1386 3.68670.1822 6.6787 0.0338 0 0 0.0455 0 0.0455 0 100 0 4 9 20.7303 13.37340.6248 22.9033 0.0886 0 0 0.0455 0 0.0455 0 100 0 4 10 8.9131 3.1940.1982 7.2642 0.0334 0 0 0.0455 0 0.0455 0 100 0 4 11 1.6189 1.2404−0.0525 −1.926 −0.0002 0 0 0.0455 0 0.0455 0 100 0 4 12 10.7432 5.7820.2838 10.4022 0.045 0 0 0.0455 0 0.0455 0 100 0 4 13 1.5884 0.8166−0.0105 −0.3833 0.0101 0 0 0.0455 0 0.0455 0 100 0 4 14 6.4031 3.23360.1734 6.3554 0.0362 0 0 0.0455 0.625 0.6705 0 6.79 93.21 4 15 15.612510.3811 0.4713 17.2763 0.0703 0 0.625 0.0455 0 0.6705 93.21 6.79 0 4 1627.9195 15.9998 0.8541 31.3081 0.1277 0.1275 0 0 0 0.1275 0 100 0 5 123.5648 16.7387 0.7605 27.8743 0.1008 0 0 0.0524 0 0.0524 0 100 0 5 224.3053 17.3486 0.7802 28.5962 0.1046 0 0 0.0524 0 0.0524 0 100 0 5 322.341 15.7024 0.7107 26.0515 0.1019 0 0 0.0524 0 0.0524 0 100 0 5 417.6158 11.8733 0.5469 20.0479 0.0791 0 0 0.0524 0 0.0524 0 100 0 5 514.2387 10.1452 0.4049 14.8406 0.0574 0 0 0.0524 0 0.0524 0 100 0 5 615.1152 10.7747 0.4328 15.8622 0.0615 0 0 0.0524 0 0.0524 0 100 0 5 76.2094 5.1538 0.1363 4.9969 0.0249 0 0 0.0524 0 0.0524 0 100 0 5 87.6993 4.4249 0.2079 7.6192 0.0348 0 0 0.0524 0 0.0524 0 100 0 5 920.3032 12.9878 0.6687 24.5092 0.091 0 0 0.0524 0 0.0524 0 100 0 5 1010.467 7.0359 0.2642 9.6824 0.0427 0 0 0.0524 0 0.0524 0 100 0 5 112.8488 0.9928 −0.0496 −1.8191 −0.0034 0 0 0.0524 0 0.0524 0 100 0 5 128.6081 4.7427 0.2975 10.9032 0.0379 0 0 0.0524 0 0.0524 0 100 0 5 132.4786 0.2441 −0.0353 −1.2925 0.0105 0 0 0.0524 0 0.0524 0 100 0 5 145.1083 3.0311 0.1416 5.192 0.0285 0 0 0.0524 0.625 0.6774 0 7.73 92.27 515 11.8585 7.5495 0.3716 13.62 0.0576 0 0.625 0.0524 0 0.6774 92.27 7.730 5 16 0.172 0.0674 −0.0092 −0.3389 0.01 0 0 0 0 0 0 0 0 6 1 22.854815.2481 0.7655 28.0601 0.1096 0 0 0.0592 0 0.0592 0 100 0 6 2 25.420516.425 0.8006 29.3446 0.11 0 0 0.0592 0 0.0592 0 100 0 6 3 25.035916.7118 0.7742 28.379 0.1081 0 0 0.0592 0 0.0592 0 100 0 6 4 19.824213.56 0.6037 22.1285 0.0864 0 0 0.0592 0 0.0592 0 100 0 6 5 15.566710.9252 0.4506 16.5181 0.0668 0 0 0.0592 0 0.0592 0 100 0 6 6 14.92489.1668 0.4848 17.7684 0.0716 0 0 0.0592 0 0.0592 0 100 0 6 7 6.27484.0969 0.1824 6.6868 0.0317 0 0 0.0592 0 0.0592 0 100 0 6 8 8.48585.8883 0.251 9.2019 0.0404 0 0 0.0592 0 0.0592 0 100 0 6 9 21.002712.7923 0.7581 27.7862 0.1015 0 0 0.0592 0 0.0592 0 100 0 6 10 4.18641.0991 0.2231 8.177 0.044 0 0 0.0592 0 0.0592 0 100 0 6 11 −1.2373−1.4393 0.0135 0.4931 0.0092 0 0 0.0592 0 0.0592 0 100 0 6 12 10.62866.8786 0.3149 11.5433 0.0492 0 0 0.0592 0 0.0592 0 100 0 6 13 1.07160.1767 0.0081 0.2959 0.0131 0 0 0.0592 0 0.0592 0 100 0 6 14 6.69594.4786 0.1742 6.3849 0.0291 0 0 0.0592 0.625 0.6842 0 8.65 91.35 6 1514.9263 8.9373 0.4504 16.5076 0.0691 0 0.625 0.0592 0 0.6842 91.35 8.650 6 16 0.9734 0.524 −0.0068 −0.2476 0.0095 0 0 0 0 0 0 0 0 7 1 22.541815.4759 0.726 26.6121 0.0978 0 0 0.066 0 0.066 0 100 0 7 2 25.335217.1813 0.8109 29.7233 0.1123 0 0 0.066 0 0.066 0 100 0 7 3 25.457517.3091 0.7912 29.0012 0.1094 0 0 0.066 0 0.066 0 100 0 7 4 20.657214.3391 0.6313 23.1392 0.0896 0 0 0.066 0 0.066 0 100 0 7 5 15.93211.3449 0.4504 16.51 0.0654 0 0 0.066 0 0.066 0 100 0 7 6 15.786211.3444 0.4701 17.2316 0.0672 0 0 0.066 0 0.066 0 100 0 7 7 6.55185.4328 0.1609 5.8983 0.0264 0 0 0.066 0 0.066 0 100 0 7 8 8.798 5.74770.2274 8.3369 0.0394 0 0 0.066 0 0.066 0 100 0 7 9 23.0075 15.39250.6659 24.4074 0.0863 0 0 0.066 0 0.066 0 100 0 7 10 9.2334 7.39960.2983 10.934 0.0356 0 0 0.066 0 0.066 0 100 0 7 11 0.7033 0.897 −0.0323−1.1825 0.0007 0 0 0.066 0 0.066 0 100 0 7 12 9.8812 6.9932 0.310611.3832 0.047 0 0 0.066 0 0.066 0 100 0 7 13 1.8315 1.5281 −0.0004−0.0142 0.0064 0 0 0.066 0 0.066 0 100 0 7 14 5.9233 4.0164 0.13464.9347 0.024 0 0 0.066 0.625 0.691 0 9.55 90.45 7 15 11.3981 7.03520.3499 12.8255 0.0508 0 0.625 0.066 0 0.691 90.45 9.55 0 7 16 26.566916.7815 0.8474 31.0624 0.1182 0.1275 0 0 0 0.1275 0 100 0 8 1 22.720115.0948 0.694 25.4388 0.0942 0 0 0.0729 0 0.0729 0 100 0 8 2 25.596816.5345 0.8165 29.9286 0.1106 0 0 0.0729 0 0.0729 0 100 0 8 3 26.901516.5093 0.8118 29.7556 0.1132 0 0 0.0729 0 0.0729 0 100 0 8 4 22.691214.399 0.6735 24.6849 0.0922 0 0 0.0729 0 0.0729 0 100 0 8 5 16.151310.0868 0.4873 17.8622 0.0711 0 0 0.0729 0 0.0729 0 100 0 8 6 14.96049.3549 0.5104 18.7093 0.0788 0 0 0.0729 0 0.0729 0 100 0 8 7 9.11064.8845 0.1351 4.9537 0.0227 0 0 0.0729 0 0.0729 0 100 0 8 8 11.64454.2759 0.265 9.7129 0.0431 0 0 0.0729 0 0.0729 0 100 0 8 9 22.149613.0101 0.7517 27.5537 0.103 0 0 0.0729 0 0.0729 0 100 0 8 10 10.75747.0805 0.323 11.8395 0.0477 0 0 0.0729 0 0.0729 0 100 0 8 11 3.60040.9577 0.0383 1.4029 0.0094 0 0 0.0729 0 0.0729 0 100 0 8 12 11.5347.8883 0.3533 12.9484 0.0508 0 0 0.0729 0 0.0729 0 100 0 8 13 1.34640.5169 −0.0012 −0.0457 0.0054 0 0 0.0729 0 0.0729 0 100 0 8 14 6.40943.371 0.1695 6.2144 0.0276 0 0 0.0729 0.625 0.6979 0 10.44 89.56 8 1512.8137 8.3353 0.3838 14.067 0.054 0 0.625 0.0729 0 0.6979 89.56 10.44 08 16 0.6005 0.7618 −0.0245 −0.8983 0.0023 0 0 0 0 0 0 0 0 9 1 22.495714.7378 0.6826 25.0193 0.0926 0 0 0.0797 0 0.0797 0 100 0 9 2 25.98617.2218 0.8042 29.4787 0.1075 0 0 0.0797 0 0.0797 0 100 0 9 3 26.727817.0659 0.8299 30.4191 0.1155 0 0 0.0797 0 0.0797 0 100 0 9 4 21.782514.3953 0.6911 25.3306 0.0965 0 0 0.0797 0 0.0797 0 100 0 9 5 17.250811.3087 0.5012 18.3711 0.0717 0 0 0.0797 0 0.0797 0 100 0 9 6 16.958110.5872 0.4639 17.0022 0.0651 0 0 0.0797 0 0.0797 0 100 0 9 7 6.33354.0566 0.1665 6.1027 0.0326 0 0 0.0797 0 0.0797 0 100 0 9 8 11.94486.8015 0.2794 10.2426 0.0347 0 0 0.0797 0 0.0797 0 100 0 9 9 22.368214.3068 0.6953 25.4874 0.0927 0 0 0.0797 0 0.0797 0 100 0 9 10 10.63956.5727 0.3015 11.0498 0.0426 0 0 0.0797 0 0.0797 0 100 0 9 11 0.7463−0.5268 −0.0297 −1.0885 0.0037 0 0 0.0797 0 0.0797 0 100 0 9 12 11.64366.9032 0.3308 12.1271 0.0465 0 0 0.0797 0 0.0797 0 100 0 9 13 2.27341.3731 −0.0036 −0.1307 0.0063 0 0 0.0797 0 0.0797 0 100 0 9 14 5.24732.3383 0.133 4.8766 0.0256 0 0 0.0797 0.625 0.7047 0 11.31 88.69 9 1514.1744 8.1484 0.4386 16.0753 0.0629 0 0.625 0.0797 0 0.7047 88.69 11.310 9 16 1.1167 0.6406 −0.0074 −0.2708 0.0074 0 0 0 0 0 0 0 0 10 1 21.070614.7112 0.6846 25.0928 0.0968 0 0 0.0865 0 0.0865 0 100 0 10 2 26.886917.9825 0.8859 32.4724 0.1184 0 0 0.0865 0 0.0865 0 100 0 10 3 26.681316.9521 0.9023 33.0744 0.1263 0 0 0.0865 0 0.0865 0 100 0 10 4 22.852614.0275 0.7543 27.65 0.106 0 0 0.0865 0 0.0865 0 100 0 10 5 16.46439.638 0.5121 18.772 0.0768 0 0 0.0865 0 0.0865 0 100 0 10 6 16.97410.2305 0.4989 18.2853 0.0738 0 0 0.0865 0 0.0865 0 100 0 10 7 7.07643.7892 0.217 7.954 0.0367 0 0 0.0865 0 0.0865 0 100 0 10 8 10.33017.0156 0.3079 11.2846 0.0444 0 0 0.0865 0 0.0865 0 100 0 10 9 22.926514.8712 0.7519 27.5603 0.1024 0 0 0.0865 0 0.0865 0 100 0 10 10 12.46776.9963 0.3574 13.1014 0.0529 0 0 0.0865 0 0.0865 0 100 0 10 11 0.5969−0.5299 −0.0215 −0.7876 0.0033 0 0 0.0865 0 0.0865 0 100 0 10 12 13.33248.0107 0.3981 14.593 0.0579 0 0 0.0865 0 0.0865 0 100 0 10 13 1.90310.5698 0.0129 0.4715 0.0076 0 0 0.0865 0 0.0865 0 100 0 10 14 6.48473.7801 0.156 5.7172 0.0292 0 0 0.0865 0.625 0.7115 0 12.16 87.84 10 1513.3979 8.7146 0.4385 16.0738 0.0621 0 0.625 0.0865 0 0.7115 87.84 12.160 10 16 25.4495 16.0477 0.8342 30.5766 0.1176 0.1275 0 0 0 0.1275 0 1000 11 1 20.1375 13.3902 0.695 25.4752 0.0941 0 0 0.0933 0 0.0933 0 100 011 2 27.139 17.1786 0.8841 32.4048 0.1236 0 0 0.0933 0 0.0933 0 100 0 113 26.9388 16.683 0.9125 33.4483 0.127 0 0 0.0933 0 0.0933 0 100 0 11 424.5762 15.8875 0.789 28.9207 0.1089 0 0 0.0933 0 0.0933 0 100 0 11 515.1923 9.882 0.4773 17.4944 0.0718 0 0 0.0933 0 0.0933 0 100 0 11 615.7362 10.517 0.4959 18.1782 0.0704 0 0 0.0933 0 0.0933 0 100 0 11 76.9524 4.547 0.2149 7.8771 0.0338 0 0 0.0933 0 0.0933 0 100 0 11 810.7228 5.8543 0.3063 11.2265 0.0473 0 0 0.0933 0 0.0933 0 100 0 11 921.6871 13.7234 0.7381 27.0563 0.1017 0 0 0.0933 0 0.0933 0 100 0 11 1010.2552 6.749 0.3273 11.9961 0.0462 0 0 0.0933 0 0.0933 0 100 0 11 110.1751 −0.8137 −0.0162 −0.5948 0.0093 0 0 0.0933 0 0.0933 0 100 0 11 1212.9233 7.3461 0.3959 14.5118 0.058 0 0 0.0933 0 0.0933 0 100 0 11 132.1161 −0.0461 0.0196 0.7173 0.0121 0 0 0.0933 0 0.0933 0 100 0 11 145.318 2.5839 0.1421 5.2076 0.028 0 0 0.0933 0.625 0.7183 0 12.99 87.0111 15 12.7569 6.3017 0.3941 14.4456 0.0579 0 0.625 0.0933 0 0.7183 87.0112.99 0 11 16 0.8455 −1.3583 0.0027 0.0985 0.0084 0 0 0 0 0 0 0 0 12 115.9884 10.3576 0.5209 19.0939 0.0763 0 0 0.1002 0 0.1002 0 100 0 12 227.3984 16.7714 0.9241 33.8719 0.128 0 0 0.1002 0 0.1002 0 100 0 12 328.1625 17.4315 0.9325 34.1804 0.1313 0 0 0.1002 0 0.1002 0 100 0 12 424.8213 15.2594 0.851 31.1941 0.1246 0 0 0.1002 0 0.1002 0 100 0 12 516.5105 9.4519 0.5715 20.9463 0.089 0 0 0.1002 0 0.1002 0 100 0 12 616.2367 8.6629 0.5246 19.229 0.0791 0 0 0.1002 0 0.1002 0 100 0 12 77.0822 2.7268 0.2494 9.143 0.0433 0 0 0.1002 0 0.1002 0 100 0 12 811.1025 6.1665 0.3763 13.7941 0.056 0 0 0.1002 0 0.1002 0 100 0 12 923.5429 14.4559 0.8026 29.419 0.1129 0 0 0.1002 0 0.1002 0 100 0 12 1012.4169 7.2141 0.384 14.0754 0.0576 0 0 0.1002 0 0.1002 0 100 0 12 11−0.2192 −1.5288 −0.0114 −0.4195 0.0063 0 0 0.1002 0 0.1002 0 100 0 12 1213.2567 7.0496 0.4182 15.3281 0.0611 0 0 0.1002 0 0.1002 0 100 0 12 131.2187 −0.6308 0.0286 1.0496 0.0116 0 0 0.1002 0 0.1002 0 100 0 12 145.5276 1.9229 0.1649 6.0426 0.0328 0 0 0.1002 0.625 0.7252 0 13.81 86.1912 15 13.3469 6.2659 0.4232 15.5137 0.0634 0 0.625 0.1002 0 0.7252 86.1913.81 0 12 16 1.0083 −0.586 0.011 0.4039 0.0096 0 0 0 0 0 0 0 0 13 118.6644 11.2964 0.6506 23.8458 0.0932 0 0 0.107 0 0.107 0 100 0 13 227.845 15.9413 0.9392 34.4261 0.1308 0 0 0.107 0 0.107 0 100 0 13 327.3697 17.3186 0.9442 34.6097 0.1337 0 0 0.107 0 0.107 0 100 0 13 425.678 15.9207 0.8401 30.7915 0.1183 0 0 0.107 0 0.107 0 100 0 13 515.7945 10.0005 0.5228 19.164 0.0793 0 0 0.107 0 0.107 0 100 0 13 615.3463 9.2398 0.5087 18.6471 0.0765 0 0 0.107 0 0.107 0 100 0 13 76.7754 3.6609 0.2308 8.459 0.0396 0 0 0.107 0 0.107 0 100 0 13 8 11.6926.4553 0.3752 13.7513 0.0561 0 0 0.107 0 0.107 0 100 0 13 9 23.280913.521 0.8112 29.7353 0.1124 0 0 0.107 0 0.107 0 100 0 13 10 13.55627.5286 0.4302 15.7676 0.0624 0 0 0.107 0 0.107 0 100 0 13 11 1.1357−1.0497 −0.0258 −0.9457 0.0072 0 0 0.107 0 0.107 0 100 0 13 12 14.08927.0847 0.4404 16.1411 0.0683 0 0 0.107 0 0.107 0 100 0 13 13 1.2307−0.0972 0.0411 1.5048 0.0161 0 0 0.107 0 0.107 0 100 0 13 14 5.04731.1814 0.1519 5.5685 0.0306 0 0 0.107 0.625 0.732 0 14.62 85.38 13 1512.8894 6.9657 0.3932 14.413 0.0574 0 0.625 0.107 0 0.732 85.38 14.62 013 16 27.0196 15.8321 0.9126 33.449 0.1349 0.1275 0 0 0 0.1275 0 100 014 1 21.6824 14.5808 0.7642 28.0108 0.1054 0 0 0.1138 0 0.1138 0 100 014 2 27.9534 18.5673 0.9122 33.4357 0.1269 0 0 0.1138 0 0.1138 0 100 014 3 28.3871 17.6025 0.9506 34.8433 0.1361 0 0 0.1138 0 0.1138 0 100 014 4 26.5322 15.1329 0.8627 31.6204 0.1283 0 0 0.1138 0 0.1138 0 100 014 5 17.27 10.4633 0.5486 20.1091 0.0846 0 0 0.1138 0 0.1138 0 100 0 146 16.6826 9.6418 0.5721 20.9704 0.0848 0 0 0.1138 0 0.1138 0 100 0 14 77.7667 4.5307 0.2694 9.8752 0.0433 0 0 0.1138 0 0.1138 0 100 0 14 813.2575 8.5866 0.4374 16.0317 0.064 0 0 0.1138 0 0.1138 0 100 0 14 924.5972 16.2327 0.8255 30.2566 0.1118 0 0 0.1138 0 0.1138 0 100 0 14 1014.1237 8.1483 0.478 17.5191 0.0713 0 0 0.1138 0 0.1138 0 100 0 14 11−0.172 −1.5106 −0.0204 −0.7482 0.0089 0 0 0.1138 0 0.1138 0 100 0 14 1215.8277 8.9664 0.5076 18.6043 0.0706 0 0 0.1138 0 0.1138 0 100 0 14 131.0637 −1.0104 0.0444 1.6268 0.0139 0 0 0.1138 0 0.1138 0 100 0 14 144.6635 2.3532 0.1677 6.1462 0.0296 0 0 0.1138 0.625 0.7388 0 15.41 84.5914 15 12.9488 7.3298 0.4296 15.7453 0.0651 0 0.625 0.1138 0 0.7388 84.5915.41 0 14 16 0.3061 −0.5069 −0.0065 −0.2391 0.0099 0 0 0 0 0 0 0 0 15 117.1998 12.0104 0.5755 21.0955 0.0799 0 0 0.1207 0 0.1207 0 100 0 15 227.4482 17.526 0.933 34.1967 0.1316 0 0 0.1207 0 0.1207 0 100 0 15 328.1178 18.8556 0.9242 33.8763 0.1324 0 0 0.1207 0 0.1207 0 100 0 15 426.8701 17.1463 0.856 31.3778 0.1258 0 0 0.1207 0 0.1207 0 100 0 15 517.6631 10.9667 0.5845 21.4248 0.0858 0 0 0.1207 0 0.1207 0 100 0 15 617.1402 10.8854 0.5425 19.8853 0.0798 0 0 0.1207 0 0.1207 0 100 0 15 78.2663 5.3027 0.2441 8.9487 0.0387 0 0 0.1207 0 0.1207 0 100 0 15 811.9892 6.7241 0.3904 14.3081 0.0566 0 0 0.1207 0 0.1207 0 100 0 15 924.1606 15.639 0.8291 30.3902 0.1118 0 0 0.1207 0 0.1207 0 100 0 15 1015.0377 10.3936 0.4614 16.9136 0.0638 0 0 0.1207 0 0.1207 0 100 0 15 110.2191 −0.9933 −0.0152 −0.558 0.0074 0 0 0.1207 0 0.1207 0 100 0 15 1216.1138 9.1228 0.5094 18.6707 0.0732 0 0 0.1207 0 0.1207 0 100 0 15 132.4821 0.3422 0.0309 1.1317 0.0144 0 0 0.1207 0 0.1207 0 100 0 15 145.4454 0.6463 0.189 6.9276 0.035 0 0 0.1207 0.625 0.7457 0 16.18 83.8215 15 14.0229 7.8558 0.4492 16.4654 0.0681 0 0.625 0.1207 0 0.7457 83.8216.18 0 15 16 0.4686 −0.7131 0.0197 0.7216 0.01 0 0 0 0 0 0 0 0 16 17.4861 4.4402 0.2493 9.1386 0.0401 0 0 0.1275 0 0.1275 0 100 0 16 229.0506 17.8613 0.9483 34.7579 0.1412 0 0 0.1275 0 0.1275 0 100 0 16 329.4694 17.4993 0.9236 33.8554 0.1479 0 0 0.1275 0 0.1275 0 100 0 16 428.4749 16.4322 0.9104 33.3693 0.1531 0 0 0.1275 0 0.1275 0 100 0 16 522.0326 12.6858 0.7055 25.8606 0.1115 0 0 0.1275 0 0.1275 0 100 0 16 620.0805 12.1402 0.6291 23.0594 0.0943 0 0 0.1275 0 0.1275 0 100 0 16 79.0587 5.2161 0.2666 9.7703 0.0461 0 0 0.1275 0 0.1275 0 100 0 16 813.983 9.3075 0.4391 16.0948 0.0636 0 0 0.1275 0 0.1275 0 100 0 16 926.9905 17.0719 0.877 32.1456 0.1198 0 0 0.1275 0 0.1275 0 100 0 16 1014.704 8.6762 0.4886 17.9102 0.073 0 0 0.1275 0 0.1275 0 100 0 16 110.7191 −1.4742 −0.0041 −0.1519 0.0077 0 0 0.1275 0 0.1275 0 100 0 16 1219.314 11.1355 0.6495 23.808 0.0899 0 0 0.1275 0 0.1275 0 100 0 16 132.4636 0.033 0.0679 2.4886 0.0206 0 0 0.1275 0 0.1275 0 100 0 16 1411.4461 6.8975 0.3856 14.134 0.0639 0 0 0.1275 0.625 0.7525 0 16.9483.06 16 15 20.8264 13.1623 0.7 25.6595 0.0961 0 0.625 0.1275 0 0.752583.06 16.94 0 16 16 26.7851 15.9945 0.9048 33.1661 0.1319 0.1275 0 0 00.1275 0 100 0 Temperature: 300 C. 1 1 26.0412 13.6761 0.7608 27.43270.1592 0.1275 0 0 0 0.1275 0 100 0 1 2 1.9716 2.4686 0.0066 0.23860.0092 0 0 0 0 0 0 0 0 1 3 0.3229 0.3952 −0.0391 −1.4081 0.0062 0 0 0 00 0 0 0 1 4 0.6417 0.8578 −0.0504 −1.8187 −0.0005 0 0 0 0 0 0 0 0 1 50.173 0.5233 −0.0449 −1.6183 0.0024 0 0 0 0 0 0 0 0 1 6 0.3624 0.0747−0.0376 −1.3546 −0.0039 0 0 0 0 0 0 0 0 1 7 26.157 12.3934 0.797 28.73830.1699 0.1275 0 0 0 0.1275 0 100 0 1 8 3.5333 0.2801 −0.0585 −2.108−0.0107 0 0 0 0 0 0 0 0 1 9 −1.8657 −3.8002 −0.0104 −0.375 0.0197 0 0 00 0 0 0 0 1 10 2.592 0.129 −0.014 −0.5051 −0.0253 0 0 0 0 0 0 0 0 1 11−3.1613 −1.397 −0.0273 −0.9858 0.0043 0 0 0 0 0 0 0 0 1 12 −0.5382−0.741 −0.0195 −0.7042 −0.0352 0 0 0 0 0 0 0 0 1 13 25.293 12.93310.8097 29.194 0.1597 0.1275 0 0 0 0.1275 0 100 0 1 14 0.8774 0.3654−0.018 −0.648 0.0052 0 0 0 0 0 0 0 0 1 15 −1.2793 0.1383 −0.0181 −0.65430.0027 0 0 0 0 0 0 0 0 1 16 25.6735 12.143 0.7277 26.2368 0.1566 0.12750 0 0 0.1275 0 100 0 2 1 14.8766 10.2106 0.3917 14.1217 0.0524 0 00.0319 0 0.0319 0 100 0 2 2 20.4545 14.6181 0.746 26.8969 0.1088 0 00.0319 0 0.0319 0 100 0 2 3 19.9352 12.3858 0.6977 25.1579 0.1196 0 00.0319 0 0.0319 0 100 0 2 4 16.0396 10.1097 0.6511 23.4768 0.109 0 00.0319 0 0.0319 0 100 0 2 5 15.904 10.2101 0.4597 16.5765 0.0626 0 00.0319 0 0.0319 0 100 0 2 6 14.9915 9.8692 0.3995 14.4034 0.0662 0 00.0319 0 0.0319 0 100 0 2 7 6.2101 5.2473 0.1852 6.6763 0.0252 0 00.0319 0 0.0319 0 100 0 2 8 9.4972 5.8339 0.283 10.205 0.0496 0 0 0.03190 0.0319 0 100 0 2 9 21.1669 13.9111 0.6435 23.2016 0.0932 0 0 0.0319 00.0319 0 100 0 2 10 8.0932 5.8934 0.2958 10.6661 0.0493 0 0 0.0319 00.0319 0 100 0 2 11 0.4906 0.3109 −0.0754 −2.7173 0.0004 0 0 0.0319 00.0319 0 100 0 2 12 12.7979 8.96 0.445 16.0439 0.0703 0 0 0.0319 00.0319 0 100 0 2 13 1.7683 2.1621 0.0286 1.0326 0.0176 0 0 0.0319 00.0319 0 100 0 2 14 11.5049 8.9483 0.3603 12.9899 0.0656 0 0 0.03190.625 0.6569 0 4.85 95.15 2 15 19.2509 11.5249 0.6541 23.5849 0.0881 00.625 0.0319 0 0.6569 95.15 4.85 0 2 16 −2.2275 0.1022 0.0038 0.1360.001 0 0 0 0 0 0 0 0 3 1 19.5625 13.7405 0.7553 27.2322 0.1169 0 00.0387 0 0.0387 0 100 0 3 2 23.3448 16.4986 0.7782 28.0599 0.1055 0 00.0387 0 0.0387 0 100 0 3 3 20.2746 14.4888 0.7447 26.8513 0.1236 0 00.0387 0 0.0387 0 100 0 3 4 21.042 14.6567 0.5975 21.5435 0.0868 0 00.0387 0 0.0387 0 100 0 3 5 15.227 11.3009 0.5184 18.6931 0.0896 0 00.0387 0 0.0387 0 100 0 3 6 16.2981 13.1574 0.4916 17.7266 0.0804 0 00.0387 0 0.0387 0 100 0 3 7 7.5318 7.7146 0.2177 7.8495 0.0364 0 00.0387 0 0.0387 0 100 0 3 8 14.1025 10.9954 0.419 15.1061 0.0628 0 00.0387 0 0.0387 0 100 0 3 9 20.9253 15.3432 0.7024 25.3266 0.1019 0 00.0387 0 0.0387 0 100 0 3 10 13.728 11.1605 0.4466 16.1033 0.0679 0 00.0387 0 0.0387 0 100 0 3 11 −1.0656 0.7638 −0.03 −1.0824 −0.001 0 00.0387 0 0.0387 0 100 0 3 12 12.0316 9.0087 0.4143 14.9372 0.064 0 00.0387 0 0.0387 0 100 0 3 13 2.3735 2.427 0.0472 1.7003 0.0158 0 00.0387 0 0.0387 0 100 0 3 14 10.011 6.6184 0.4321 15.5784 0.078 0 00.0387 0.625 0.6637 0 5.83 94.17 3 15 17.1288 11.9418 0.6936 25.00810.1016 0 0.625 0.0387 0 0.6637 94.17 5.83 0 3 16 −0.0207 −0.0056 0.05642.0341 −0.003 0 0 0 0 0 0 0 0 4 1 23.9972 15.9845 0.7717 27.8233 0.119 00 0.0455 0 0.0455 0 100 0 4 2 24.3635 16.2531 0.7072 25.5007 0.1199 0 00.0455 0 0.0455 0 100 0 4 3 21.4425 14.1432 0.7498 27.0362 0.1265 0 00.0455 0 0.0455 0 100 0 4 4 19.4479 12.996 0.6822 24.5996 0.107 0 00.0455 0 0.0455 0 100 0 4 5 16.0527 11.3163 0.5819 20.98 0.0935 0 00.0455 0 0.0455 0 100 0 4 6 17.5309 11.186 0.5671 20.447 0.0842 0 00.0455 0 0.0455 0 100 0 4 7 8.0993 5.7381 0.3374 12.166 0.0503 0 00.0455 0 0.0455 0 100 0 4 8 14.119 9.8107 0.5489 19.7929 0.0801 0 00.0455 0 0.0455 0 100 0 4 9 23.2762 14.9011 0.7786 28.0723 0.1033 0 00.0455 0 0.0455 0 100 0 4 10 14.7194 10.4363 0.5718 20.6185 0.08 0 00.0455 0 0.0455 0 100 0 4 11 1.1453 0.3882 −0.067 −2.4162 −0.0168 0 00.0455 0 0.0455 0 100 0 4 12 12.7656 8.8311 0.4759 17.1582 0.0689 0 00.0455 0 0.0455 0 100 0 4 13 4.4502 1.323 0.0072 0.2593 0.0135 0 00.0455 0 0.0455 0 100 0 4 14 13.3844 9.4729 0.4141 14.9311 0.0687 0 00.0455 0.625 0.6705 0 6.79 93.21 4 15 20.7018 14.4153 0.6795 24.50020.0932 0 0.625 0.0455 0 0.6705 93.21 6.79 0 4 16 26.3093 12.5646 0.740526.6988 0.1561 0.1275 0 0 0 0.1275 0 100 0 5 1 21.4105 14.4067 0.712525.6898 0.11 0 0 0.0524 0 0.0524 0 100 0 5 2 22.1022 14.8036 0.81929.5304 0.1282 0 0 0.0524 0 0.0524 0 100 0 5 3 22.5933 14.8442 0.724426.1201 0.1233 0 0 0.0524 0 0.0524 0 100 0 5 4 21.0057 13.8057 0.691124.9201 0.1153 0 0 0.0524 0 0.0524 0 100 0 5 5 17.672 12.2393 0.572820.6522 0.0902 0 0 0.0524 0 0.0524 0 100 0 5 6 16.0245 11.7967 0.590221.2789 0.0941 0 0 0.0524 0 0.0524 0 100 0 5 7 8.682 6.8022 0.35 12.61850.0569 0 0 0.0524 0 0.0524 0 100 0 5 8 16.2047 10.7313 0.5656 20.39210.0857 0 0 0.0524 0 0.0524 0 100 0 5 9 21.0729 14.0649 0.7974 28.75150.124 0 0 0.0524 0 0.0524 0 100 0 5 10 18.1655 12.1093 0.6249 22.53230.094 0 0 0.0524 0 0.0524 0 100 0 5 11 −3.2789 −1.8833 0.0173 0.625−0.017 0 0 0.0524 0 0.0524 0 100 0 5 12 12.1376 7.6528 0.5085 18.33390.0689 0 0 0.0524 0 0.0524 0 100 0 5 13 2.8719 1.6064 0.0398 1.43470.0232 0 0 0.0524 0 0.0524 0 100 0 5 14 11.6313 7.1984 0.3756 13.54420.064 0 0 0.0524 0.625 0.6774 0 7.73 92.27 5 15 18.7077 12.3422 0.678424.4596 0.1017 0 0.625 0.0524 0 0.6774 92.27 7.73 0 5 16 −0.923 0.64230.0024 0.0871 −0.0005 0 0 0 0 0 0 0 0 6 1 22.0063 14.1082 0.7772 28.02160.121 0 0 0.0592 0 0.0592 0 100 0 6 2 23.7522 14.4251 0.8181 29.49830.1363 0 0 0.0592 0 0.0592 0 100 0 6 3 23.7349 12.7968 0.778 28.05180.1487 0 0 0.0592 0 0.0592 0 100 0 6 4 21.7688 12.1769 0.7488 27.00060.1335 0 0 0.0592 0 0.0592 0 100 0 6 5 18.6185 12.368 0.6292 22.68620.1057 0 0 0.0592 0 0.0592 0 100 0 6 6 17.435 11.7025 0.6457 23.28330.0997 0 0 0.0592 0 0.0592 0 100 0 6 7 9.5496 7.4033 0.4005 14.44180.0656 0 0 0.0592 0 0.0592 0 100 0 6 8 18.8345 12.608 0.602 21.70770.0895 0 0 0.0592 0 0.0592 0 100 0 6 9 22.7783 14.5707 0.7858 28.33190.1268 0 0 0.0592 0 0.0592 0 100 0 6 10 14.2889 9.3319 0.4808 17.33440.0626 0 0 0.0592 0 0.0592 0 100 0 6 11 −1.4423 −3.1898 0.0072 0.2597−0.0242 0 0 0.0592 0 0.0592 0 100 0 6 12 14.6391 9.1343 0.5169 18.63930.0784 0 0 0.0592 0 0.0592 0 100 0 6 13 1.3924 0.1849 0.1067 3.84580.0254 0 0 0.0592 0 0.0592 0 100 0 6 14 12.4467 7.9011 0.47 16.9470.0796 0 0 0.0592 0.625 0.6842 0 8.65 91.35 6 15 20.5551 12.4877 0.724126.1085 0.1086 0 0.625 0.0592 0 0.6842 91.35 8.65 0 6 16 1.8224 1.91940.0293 1.0577 −0.001 0 0 0 0 0 0 0 0 7 1 20.1793 13.5157 0.7141 25.74830.1062 0 0 0.066 0 0.066 0 100 0 7 2 23.9199 15.0715 0.7923 28.56910.1334 0 0 0.066 0 0.066 0 100 0 7 3 24.0921 13.8724 0.7704 27.77940.1489 0 0 0.066 0 0.066 0 100 0 7 4 22.4883 13.3333 0.7472 26.94010.1331 0 0 0.066 0 0.066 0 100 0 7 5 18.3753 10.967 0.6933 24.99640.1147 0 0 0.066 0 0.066 0 100 0 7 6 19.1636 11.8882 0.594 21.41790.0973 0 0 0.066 0 0.066 0 100 0 7 7 11.6242 8.7829 0.358 12.9075 0.05890 0 0.066 0 0.066 0 100 0 7 8 18.9461 11.9304 0.6075 21.9057 0.0865 0 00.066 0 0.066 0 100 0 7 9 20.8727 13.268 0.8581 30.9391 0.1366 0 0 0.0660 0.066 0 100 0 7 10 19.7469 12.533 0.627 22.6084 0.0889 0 0 0.066 00.066 0 100 0 7 11 0.2661 −1.0746 −0.0206 −0.7417 −0.0241 0 0 0.066 00.066 0 100 0 7 12 14.9635 8.7674 0.5117 18.4485 0.0776 0 0 0.066 00.066 0 100 0 7 13 2.473 1.1259 0.0915 3.3004 0.0134 0 0 0.066 0 0.066 0100 0 7 14 10.4908 6.4436 0.4097 14.774 0.0771 0 0 0.066 0.625 0.691 09.55 90.45 7 15 17.9387 11.3159 0.7335 26.449 0.109 0 0.625 0.066 00.691 90.45 9.55 0 7 16 24.6649 12.1883 0.7892 28.4564 0.1735 0.1275 0 00 0.1275 0 100 0 8 1 20.4072 13.9072 0.7031 25.3521 0.1107 0 0 0.0729 00.0729 0 100 0 8 2 23.2299 15.5533 0.8078 29.1272 0.1368 0 0 0.0729 00.0729 0 100 0 8 3 24.3029 13.9797 0.7799 28.1203 0.1564 0 0 0.0729 00.0729 0 100 0 8 4 22.2113 14.5975 0.7495 27.0256 0.1425 0 0 0.0729 00.0729 0 100 0 8 5 18.1577 13.0692 0.6943 25.034 0.1167 0 0 0.0729 00.0729 0 100 0 8 6 16.4584 11.241 0.6799 24.5135 0.1128 0 0 0.0729 00.0729 0 100 0 8 7 11.3178 9.6452 0.4321 15.5795 0.0596 0 0 0.0729 00.0729 0 100 0 8 8 20.8336 14.4605 0.6457 23.2815 0.0922 0 0 0.0729 00.0729 0 100 0 8 9 23.346 15.3942 0.8346 30.0941 0.1169 0 0 0.0729 00.0729 0 100 0 8 10 20.3283 13.3467 0.6964 25.1102 0.1063 0 0 0.0729 00.0729 0 100 0 8 11 6.0017 3.7447 0.2344 8.4523 0.0402 0 0 0.0729 00.0729 0 100 0 8 12 14.0669 9.2173 0.572 20.6246 0.0862 0 0 0.0729 00.0729 0 100 0 8 13 0.4343 −0.3379 0.1029 3.7103 0.0224 0 0 0.0729 00.0729 0 100 0 8 14 12.9196 8.2041 0.4689 16.9054 0.0749 0 0 0.07290.625 0.6979 0 10.44 89.56 8 15 20.3025 12.6472 0.6618 23.8639 0.1 00.625 0.0729 0 0.6979 89.56 10.44 0 8 16 0.7273 0.7062 −0.0175 −0.63−0.0087 0 0 0 0 0 0 0 0 9 1 19.0866 13.801 0.6956 25.0805 0.1067 0 00.0797 0 0.0797 0 100 0 9 2 23.4011 15.4022 0.8062 29.0677 0.1362 0 00.0797 0 0.0797 0 100 0 9 3 24.2636 14.0356 0.8069 29.094 0.1585 0 00.0797 0 0.0797 0 100 0 9 4 23.0618 13.7204 0.7603 27.4122 0.137 0 00.0797 0 0.0797 0 100 0 9 5 19.2953 12.3324 0.6838 24.6546 0.1191 0 00.0797 0 0.0797 0 100 0 9 6 16.4524 11.6941 0.5833 21.033 0.0966 0 00.0797 0 0.0797 0 100 0 9 7 8.8155 6.193 0.4081 14.7154 0.0678 0 00.0797 0 0.0797 0 100 0 9 8 18.3421 12.4823 0.6492 23.4094 0.095 0 00.0797 0 0.0797 0 100 0 9 9 22.5571 15.4221 0.8241 29.7153 0.1201 0 00.0797 0 0.0797 0 100 0 9 10 18.2863 13.1397 0.6724 24.2444 0.0988 0 00.0797 0 0.0797 0 100 0 9 11 −1.5339 −0.5868 −0.0006 −0.0218 −0.0198 0 00.0797 0 0.0797 0 100 0 9 12 13.9602 9.1693 0.5547 20.0022 0.0819 0 00.0797 0 0.0797 0 100 0 9 13 1.1827 1.2849 0.1107 3.9916 0.0024 0 00.0797 0 0.0797 0 100 0 9 14 10.2757 6.1288 0.3969 14.3106 0.0711 0 00.0797 0.625 0.7047 0 11.31 88.69 9 15 19.4095 11.4849 0.732 26.39180.1116 0 0.625 0.0797 0 0.7047 88.69 11.31 0 9 16 −0.4746 0.3 0.06492.3389 0.0106 0 0 0 0 0 0 0 0 10 1 19.6155 13.2592 0.7151 25.784 0.11370 0 0.0865 0 0.0865 0 100 0 10 2 24.4255 14.2114 0.8452 30.474 0.1541 00 0.0865 0 0.0865 0 100 0 10 3 25.1167 12.0723 0.8229 29.6706 0.1783 0 00.0865 0 0.0865 0 100 0 10 4 23.9367 12.0867 0.8302 29.934 0.1595 0 00.0865 0 0.0865 0 100 0 10 5 20.499 11.2772 0.6949 25.0561 0.1257 0 00.0865 0 0.0865 0 100 0 10 6 18.4277 10.342 0.652 23.5077 0.1136 0 00.0865 0 0.0865 0 100 0 10 7 10.6829 8.2331 0.4943 17.8212 0.0797 0 00.0865 0 0.0865 0 100 0 10 8 21.0351 13.5697 0.6934 25.0025 0.1016 0 00.0865 0 0.0865 0 100 0 10 9 23.3546 15.5724 0.8319 29.9961 0.1265 0 00.0865 0 0.0865 0 100 0 10 10 20.2733 13.206 0.7226 26.0547 0.1094 0 00.0865 0 0.0865 0 100 0 10 11 −2.2709 −1.6818 −0.003 −0.1081 −0.0191 0 00.0865 0 0.0865 0 100 0 10 12 15.5394 9.154 0.5767 20.7948 0.0875 0 00.0865 0 0.0865 0 100 0 10 13 2.338 0.6958 0.1166 4.204 0.0286 0 00.0865 0 0.0865 0 100 0 10 14 11.8371 7.0502 0.4485 16.1702 0.0781 0 00.0865 0.625 0.7115 0 12.16 87.84 10 15 18.9643 11.9052 0.7159 25.81250.1082 0 0.625 0.0865 0 0.7115 87.84 12.16 0 10 16 23.3683 12.03280.7792 28.0962 0.1577 0.1275 0 0 0 0.1275 0 100 0 11 1 18.6802 11.57420.6796 24.5045 0.1057 0 0 0.0933 0 0.0933 0 100 0 11 2 25.0222 13.98630.8039 28.9852 0.1512 0 0 0.0933 0 0.0933 0 100 0 11 3 25.6394 13.12150.8122 29.2838 0.1687 0 0 0.0933 0 0.0933 0 100 0 11 4 24.6744 14.51830.7802 28.132 0.1536 0 0 0.0933 0 0.0933 0 100 0 11 5 19.3295 12.61350.685 24.6995 0.1225 0 0 0.0933 0 0.0933 0 100 0 11 6 18.7665 11.78230.6491 23.4044 0.1112 0 0 0.0933 0 0.0933 0 100 0 11 7 12.0459 8.2620.4669 16.8355 0.0746 0 0 0.0933 0 0.0933 0 100 0 11 8 19.7356 12.29240.7225 26.0526 0.1072 0 0 0.0933 0 0.0933 0 100 0 11 9 23.3494 14.41310.8518 30.7139 0.1298 0 0 0.0933 0 0.0933 0 100 0 11 10 19.1323 12.68490.7094 25.5779 0.105 0 0 0.0933 0 0.0933 0 100 0 11 11 −0.9895 −0.2695−0.004 −0.1435 −0.0127 0 0 0.0933 0 0.0933 0 100 0 11 12 14.8304 10.19630.582 20.9867 0.0899 0 0 0.0933 0 0.0933 0 100 0 11 13 2.208 2.55870.1029 3.7107 0.0204 0 0 0.0933 0 0.0933 0 100 0 11 14 10.9763 6.42660.3918 14.1258 0.0707 0 0 0.0933 0.625 0.7183 0 12.99 87.01 11 1518.1906 10.6621 0.698 25.1685 0.106 0 0.625 0.0933 0 0.7183 87.01 12.990 11 16 −0.9643 −0.7161 0.0392 1.4143 −0.0048 0 0 0 0 0 0 0 0 12 115.4588 10.1833 0.5953 21.4632 0.1001 0 0 0.1002 0 0.1002 0 100 0 12 224.7319 13.6012 0.8478 30.5688 0.161 0 0 0.1002 0 0.1002 0 100 0 12 326.8912 12.8758 0.8008 28.8754 0.1851 0 0 0.1002 0 0.1002 0 100 0 12 424.6558 12.9216 0.8196 29.5504 0.1758 0 0 0.1002 0 0.1002 0 100 0 12 520.5267 12.1018 0.7215 26.0139 0.1329 0 0 0.1002 0 0.1002 0 100 0 12 618.4287 11.4481 0.6811 24.5589 0.1172 0 0 0.1002 0 0.1002 0 100 0 12 713.4393 9.372 0.4909 17.6995 0.0793 0 0 0.1002 0 0.1002 0 100 0 12 821.0809 13.9911 0.7512 27.0875 0.111 0 0 0.1002 0 0.1002 0 100 0 12 923.772 15.0448 0.8517 30.7084 0.1339 0 0 0.1002 0 0.1002 0 100 0 12 1019.8095 12.8912 0.7381 26.6137 0.1093 0 0 0.1002 0 0.1002 0 100 0 12 11−1.4941 −1.399 −0.0134 −0.4846 −0.018 0 0 0.1002 0 0.1002 0 100 0 12 1216.0743 10.6539 0.5977 21.5507 0.092 0 0 0.1002 0 0.1002 0 100 0 12 132.0581 1.6359 0.1105 3.986 0.0298 0 0 0.1002 0 0.1002 0 100 0 12 1410.744 6.4761 0.4184 15.0852 0.076 0 0 0.1002 0.625 0.7252 0 13.81 86.1912 15 18.2843 10.3265 0.6975 25.1492 0.112 0 0.625 0.1002 0 0.7252 86.1913.81 0 12 16 −0.4083 −1.1083 0.0632 2.2805 0.02 0 0 0 0 0 0 0 0 13 117.3784 11.3659 0.6531 23.5471 0.1026 0 0 0.107 0 0.107 0 100 0 13 224.8735 13.9698 0.8645 31.1714 0.1634 0 0 0.107 0 0.107 0 100 0 13 326.731 13.2379 0.8304 29.9397 0.1799 0 0 0.107 0 0.107 0 100 0 13 425.0125 13.3208 0.8199 29.5626 0.1706 0 0 0.107 0 0.107 0 100 0 13 520.9959 12.5637 0.7 25.2389 0.1263 0 0 0.107 0 0.107 0 100 0 13 619.7859 13.0643 0.6384 23.0182 0.1112 0 0 0.107 0 0.107 0 100 0 13 712.7701 8.6484 0.4737 17.0786 0.0821 0 0 0.107 0 0.107 0 100 0 13 819.9798 12.3643 0.7421 26.7561 0.1113 0 0 0.107 0 0.107 0 100 0 13 923.9004 15.4262 0.8368 30.1725 0.1326 0 0 0.107 0 0.107 0 100 0 13 1020.1688 14.395 0.7685 27.7093 0.1134 0 0 0.107 0 0.107 0 100 0 13 11−1.5531 −0.2131 0.0003 0.0093 −0.0139 0 0 0.107 0 0.107 0 100 0 13 1216.261 10.9519 0.6007 21.66 0.0928 0 0 0.107 0 0.107 0 100 0 13 132.1579 1.7026 0.1307 4.7131 0.0287 0 0 0.107 0 0.107 0 100 0 13 1410.3449 7.0881 0.4013 14.4697 0.0725 0 0 0.107 0.625 0.732 0 14.62 85.3813 15 17.9906 12.3676 0.6892 24.8485 0.1057 0 0.625 0.107 0 0.732 85.3814.62 0 13 16 24.9296 12.3107 0.7853 28.3135 0.1895 0.1275 0 0 0 0.12750 100 0 14 1 19.7006 13.895 0.7196 25.9447 0.1225 0 0 0.1138 0 0.1138 0100 0 14 2 24.628 13.7864 0.8645 31.1715 0.1715 0 0 0.1138 0 0.1138 0100 0 14 3 27.0603 12.7211 0.8226 29.6605 0.2007 0 0 0.1138 0 0.1138 0100 0 14 4 24.9719 12.0514 0.83 29.9259 0.1896 0 0 0.1138 0 0.1138 0 1000 14 5 20.0669 11.3486 0.7334 26.4431 0.1416 0 0 0.1138 0 0.1138 0 100 014 6 19.3148 11.3116 0.7073 25.5033 0.128 0 0 0.1138 0 0.1138 0 100 0 147 13.0698 9.2496 0.5178 18.6703 0.0862 0 0 0.1138 0 0.1138 0 100 0 14 821.4825 14.0766 0.7634 27.5263 0.1153 0 0 0.1138 0 0.1138 0 100 0 14 923.8379 15.3459 0.8607 31.0347 0.1367 0 0 0.1138 0 0.1138 0 100 0 14 1021.5278 13.8928 0.7851 28.3081 0.1137 0 0 0.1138 0 0.1138 0 100 0 14 11−2.1621 −1.2165 −0.0091 −0.3271 −0.0078 0 0 0.1138 0 0.1138 0 100 0 1412 17.3041 11.5725 0.646 23.2923 0.0958 0 0 0.1138 0 0.1138 0 100 0 1413 1.949 2.0565 0.0896 3.2302 0.028 0 0 0.1138 0 0.1138 0 100 0 14 149.3689 6.5087 0.3449 12.4353 0.0636 0 0 0.1138 0.625 0.7388 0 15.4184.59 14 15 18.4324 12.0276 0.6914 24.9297 0.1067 0 0.625 0.1138 00.7388 84.59 15.41 0 14 16 −0.7558 −0.6898 0.0165 0.5934 0.0011 0 0 0 00 0 0 0 15 1 18.1472 11.9418 0.6987 25.1939 0.1082 0 0 0.1207 0 0.1207 0100 0 15 2 24.7631 13.6604 0.8641 31.1563 0.1697 0 0 0.1207 0 0.1207 0100 0 15 3 26.1211 11.8227 0.834 30.0705 0.2037 0 0 0.1207 0 0.1207 0100 0 15 4 24.5677 11.9552 0.7923 28.5692 0.1875 0 0 0.1207 0 0.1207 0100 0 15 5 20.0898 11.474 0.7193 25.9371 0.144 0 0 0.1207 0 0.1207 0 1000 15 6 19.3675 11.6613 0.6822 24.5972 0.1254 0 0 0.1207 0 0.1207 0 100 015 7 12.9911 8.3415 0.5124 18.477 0.0905 0 0 0.1207 0 0.1207 0 100 0 158 19.4851 12.9013 0.711 25.6353 0.1146 0 0 0.1207 0 0.1207 0 100 0 15 923.6077 14.5462 0.8618 31.074 0.1436 0 0 0.1207 0 0.1207 0 100 0 15 1021.2589 13.7735 0.7922 28.5624 0.1207 0 0 0.1207 0 0.1207 0 100 0 15 11−1.3789 −1.3203 0.0019 0.0686 −0.0106 0 0 0.1207 0 0.1207 0 100 0 15 1216.8366 10.3498 0.6489 23.3953 0.1014 0 0 0.1207 0 0.1207 0 100 0 15 132.5374 0.8067 0.138 4.9742 0.0357 0 0 0.1207 0 0.1207 0 100 0 15 1411.1396 7.0915 0.4088 14.741 0.0773 0 0 0.1207 0.625 0.7457 0 16.1883.82 15 15 17.5426 10.4944 0.7045 25.4019 0.1136 0 0.625 0.1207 00.7457 83.82 16.18 0 15 16 −0.4051 −0.4444 0.0729 2.6294 0.0112 0 0 0 00 0 0 0 16 1 15.0725 8.0994 0.5869 21.1613 0.0985 0 0 0.1275 0 0.1275 0100 0 16 2 24.67 8.6858 0.7009 25.2716 0.2051 0 0 0.1275 0 0.1275 0 1000 16 3 27.4278 6.3099 0.707 25.4923 0.2645 0 0 0.1275 0 0.1275 0 100 016 4 24.8032 6.1186 0.6967 25.1217 0.2372 0 0 0.1275 0 0.1275 0 100 0 165 20.9479 7.854 0.6707 24.1843 0.1784 0 0 0.1275 0 0.1275 0 100 0 16 619.4346 9.972 0.6893 24.8548 0.1408 0 0 0.1275 0 0.1275 0 100 0 16 714.3144 8.9315 0.5183 18.6864 0.0889 0 0 0.1275 0 0.1275 0 100 0 16 820.6449 13.6205 0.7023 25.3217 0.1142 0 0 0.1275 0 0.1275 0 100 0 16 924.2561 14.785 0.854 30.7919 0.1506 0 0 0.1275 0 0.1275 0 100 0 16 1021.0486 14.0733 0.6995 25.2209 0.1084 0 0 0.1275 0 0.1275 0 100 0 16 11−2.2759 −0.0846 0.0413 1.4879 0.024 0 0 0.1275 0 0.1275 0 100 0 16 1217.1423 10.7518 0.5869 21.1613 0.0898 0 0 0.1275 0 0.1275 0 100 0 16 133.0092 2.0883 0.2069 7.4586 0.0432 0 0 0.1275 0 0.1275 0 100 0 16 1412.8714 7.6083 0.5142 18.5415 0.1069 0 0 0.1275 0.625 0.7525 0 16.9483.06 16 15 17.5841 9.9481 0.6294 22.6946 0.129 0 0.625 0.1275 0 0.752583.06 16.94 0 16 16 25.0686 11.1805 0.8288 29.884 0.1822 0.1275 0 0 00.1275 0 100 0

1. A catalyst for catalyzing the water gas shift reaction consisting essentially of: a) Ru, its oxides or mixtures thereof; b) Co, its oxides or mixtures thereof; and c) Mo, its oxides or mixtures thereof; wherein the catalyst has an essential absence of Pt.
 2. A catalyst according to claim 1, wherein the catalyst is supported on a carrier comprising at least one member selected from the group consisting of alumina, zirconia, titania, ceria, magnesia, lanthania, niobia, zeolite, perovskite, silica clay, yttria, iron oxide and mixtures thereof.
 3. A catalyst according to claim 2, wherein the carrier comprises at least one member selected from the group consisting of zirconia, titania and ceria.
 4. A catalyst according to claim 1, wherein the supported water gas shift catalyst comprises between about 0.01 wt. % to about 10 wt. % with respect to the total weight of all catalyst components plus the support material, of each of Ru, and Co, respectively, in the water gas shift catalyst.
 5. A catalyst according to claim 1, wherein the water gas shift catalyst comprises between about 0.05 wt. % to about 20 wt. % with respect to the total weight of all catalyst components plus the support material, of each of Ru, Co, and Mo, respectively in the water gas shift catalyst.
 6. A catalyst for catalyzing the water gas shift reaction consisting essentially of: a) Ru, its oxides or mixtures thereof; b) Co, its oxides or mixtures thereof; c) Mo, its oxides or mixtures thereof; and d) at least one of Li, Na, Rb, Cs, Ti, Zr, Cr, Fe, La, Ce, Eu, their oxides and mixtures thereof, wherein the catalyst has an essential absence of Pt.
 7. A catalyst according to claim 6, wherein the catalyst is supported on a carrier comprising at least one member selected from the group consisting of alumina, zirconia, titania, ceria, magnesia, lanthania, niobia, zeolite, perovskite, silica clay, yttria, iron oxide and mixtures thereof.
 8. A catalyst according to claim 7, wherein the carrier comprises at least one member selected from the group consisting of zirconia, titania and ceria.
 9. A catalyst according to claim 6, wherein the supported water gas shift catalyst comprises between about 0.01 wt. % to about 10 wt. % with respect to the total weight of all catalyst components plus the support material, of each of Ru and Co, respectively, in the water gas shift catalyst.
 10. A catalyst according to claim 6, wherein the water gas shift catalyst comprises between about 0.05 wt. % to about 20 wt. % with respect to the total weight of all catalyst components plus the support material, of each of Ru, Co, Mo, Ti, Zr, Cr, Fe, La, Ce and Eu, respectively, present in the water gas shift catalyst. 